Combined cracking and selective hydrogen combustion for catalytic cracking

ABSTRACT

A catalyst system and process for combined cracking and selective hydrogen combustion of hydrocarbons are disclosed. The catalyst system contains at least one solid acid component and at least one metal-based component which consists of (a) oxygen and/or sulfur and (b) a metal combination selected from the group consisting of:  
     i) at least one metal from Group 3 and at least one metal from Groups 4-15 of the Periodic Table of the Elements;  
     ii) at least one metal from Groups 5-15 of the Periodic Table of the Elements, and at least one metal from at least one of Groups 1, 2, and 4 of the Periodic Table of the Elements;  
     iii) at least one metal from Groups 1 and 2, at least one metal from Group 3, and at least one metal from Groups 4-15 of the Periodic Table of the Elements; and  
     iv) two or more metals from Groups 4-15 of the Periodic Table of the Elements,  
     wherein the at least one of oxygen and sulfur is chemically bound both within and between the metals and, optionally, (3) at least one of at least one support, at least one filler and at least one binder. The process is such that the yield of hydrogen is less than the yield of hydrogen when contacting the hydrocarbons with the solid acid component alone. Further the emissions of NO x  from the regeneration cycle of the catalyst system are reduced.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a Continuation-in-Part which claims priorityto applications U.S. Ser. No. 10/369,880, filed Feb. 20, 2003; U.S. Ser.No. 10/358,569; filed Feb. 5, 2003, U.S. Ser. No. 10/358,564, filed Feb.5, 2003; and U.S. Ser. No. 10/358,977, filed Feb. 5, 2003; each of whichis hereby fully incorporated by reference.

FIELD OF THE INVENTION

[0002] The present invention relates to a novel catalyst composition andits use in a novel hydrocarbon cracking process. The catalyst isparticularly useful in reducing the concentration of hydrogen incracking products and in reducing the emission of nitrogen oxides duringcatalyst regeneration.

DISCUSSION OF BACKGROUND INFORMATION

[0003] Current cracking technologies for the production of light olefins(e.g., ethylene, propylene, and butylenes), gasoline and other crackedproducts such as light paraffins and naphtha can be classified into thetwo categories of thermal cracking (also known as steam cracking) andcatalytic cracking. While these technologies have been practiced formany years and are considered the workhorses for light olefinproduction, both have disadvantages.

[0004] Steam or thermal cracking, a robust technology that does notutilize catalyst, produces the more valuable ethylene as the primarylight olefin product. It is particularly suitable for crackingparaffinic feedstreams to a wide range of products including hydrogen,light olefins, light paraffins, and heavier liquid hydrocarbon productssuch as pyrolysis gasoline and steam cracked gas oil. However, steamcracking is an expensive, complex technology due to required specialconstruction material to sustain high cracking temperatures (˜850° C.)and high energy input. Sulfur addition is required to passivate thefurnace metal surfaces on a continuous basis, creating such undesirableside effects as environmental and product contamination. Steam crackingis not considered to be suitable for cracking feeds containing highconcentrations of light olefins as it makes high levels of low valueheavy by-products due to the more reactive nature of the olefin feeds.In addition, steam cracking makes a relatively low amount of propylene,and, therefore, is not considered suitable for meeting the anticipatedgrowing demand for propylene in the future. Also, steam crackingrequires steam dilution to control product selectivity and to maintainan acceptable run length; steam dilution is costly in terms of capitalinvestment and energy consumption.

[0005] Current catalytic cracking technologies employ solid acidcatalysts such as zeolites to promote cracking reactions. Unlike steamcracking technology, propylene is the primary light olefin product ofcatalytic cracking. Accordingly, catalytic cracking would be consideredas the main source for growing propylene demand. Catalytic cracking canbe classified into the following two general categories. The firstcategory is Fluid Catalytic Cracking (FCC), which is the preferredrefining process for converting higher boiling petroleum fractions intolower boiling products, such as gasoline, cracked naphtha and lightolefins. The FCC catalyst of fine particles acts like a fluid andcirculates in a closed cycle between a cracking reactor and a separateregenerator. In general, FCC catalysts can be classified into twocategories—FCC base catalysts and FCC additive catalysts. Typical FCCcatalysts contain the base catalysts which comprise a zeolite componentand a matrix component. The zeolite is a major contributor for thecatalyst activity, selectivity and stability. Examples of the zeolitecomponent include Y zeolite and beta zeolite. The zeolite usually istreated with various modifications such as dealumination, rare earthexchange, or phosphorous treatment. Examples of typical matrix materialsinclude amorphous compounds such as silica, alumina, silica-alumina,silica-magnesia, and clays such as kaolinite, halloysite, ormontmorillonite. The matrix component can serve several purposes. It canbe used to bind the zeolite component to form catalyst particles. It canserve as a diffusion medium for the transport of feed and productmolecules. It also can act as a filler which dilutes the zeoliteparticles to moderate the catalyst activity. In addition, the matrix canhelp heat transfer.

[0006] Some FCC catalysts also contain FCC additive catalyst(s),including, by way of non-limiting examples, octane-boosting additives,metal passivation additives, SOx reduction additives, NOx reductionadditives, CO oxidation additives, and coke oxidation additives. Theadditive catalyst(s) can be either incorporated into the base catalystmatrix or used as separate catalyst particles. When used as separatecatalyst particles, the additive catalyst(s) will contain in addition tothe catalytic active components their own matrix materials, which may ormay not be the same as the base catalyst matrix. Examples (U.S. Pat. No.4,368,114, which is incorporated herein by reference in its entirety) ofthe main catalytic components for octane-boosting additive catalystsinclude ZSM-5 zeolite, ZSM-11 zeolite, and beta zeolite. Examples of SOxreduction additives include magnesia, ceria-alumina, and rare earths onalumina. Examples of CO oxidation additives include platinum and/orpalladium either directly added to the base catalyst at trace levels ordispersed on a support such as alumina or silica alumina (U.S. Pat. Nos.4,072,600 and 4,107,032, which are incorporated herein by reference intheir entirety). Non-limiting examples of coke oxidation promotersinclude lanthanum and iron embedded in the base catalyst (U.S. Pat. No.4,137,151, which is incorporated herein by reference in its entirety).Examples of metal passivation additives include barium titanium oxide(U.S. Pat. No. 4,810,358, which is incorporated herein by reference inits entirety), calcium-containing additives selected from the groupconsisting of calcium-titanium, calcium-zirconium,calcium-titanium-zirconium oxides and mixtures thereof (U.S. Pat. No.4,451,355, which is incorporated herein by reference in its entirety),and antimony and/or tin on magnesium-containing clays (U.S. Pat. No.4,466,884, which is incorporated herein by reference in its entirety).

[0007] For a riser FCC unit, fresh feed contacts hot catalyst from theregenerator at the base of the riser reactor. The cracked products aredischarged from the riser to pass through a main column, which producesseveral liquid streams and a vapor stream containing hydrogen, methane,ethane, propane, butane, and light olefins. The vapor stream iscompressed in a wet gas compressor and charged to the unsaturated gasfacility for product purification. Another technology in this categoryis moving bed cracking or Thermofor Catalytic Cracking (TCC). The TCCcatalyst is in the form of small beads, which circulate between areactor and a regenerator in the form of a moving bed. A furtherdescription of the FCC process may be found in the monograph, “FluidCatalytic Cracking with Zeolite Catalysts,” P. B. Venuto and E. T.Habib, Marcel Dekker, New York, 1978, incorporated by reference.

[0008] The second category of catalytic cracking is catalytic crackingof naphtha, the main purpose of which is the generation of lightolefins. Either FCC-type reactor/regenerator technology (U.S. Pat. No.5,043,522, which is incorporated herein by reference in its entirety),or fixed-bed reactor technology (EP0921175A1 and EP0921179A1, which areincorporated herein by reference in their entirety), can be used. Theproducts, which include liquid streams and a vapor stream of hydrogen,methane, ethane, propane, butane, and light olefins go through a seriesof treatments similar to that for the FCC products.

[0009] As pointed out above, current cracking technologies typicallyproduce vapor streams containing mixtures of hydrogen, light paraffins(e.g., methane, ethane, propane, and butanes) and light olefins. In somecases, such as ethane cracking, hydrogen is recovered in high purity asa valued product. In many other cases, such as steam cracking ofnaphtha, FCC of gas oil, and catalytic cracking of olefinic naphtha,hydrogen is undesirable due to the difficulty of separating H₂ from thelight olefins (ethylene and propylene). The presence of even a moderatequantity of H₂ in cracked products necessitates such expensive equipmentas multi-stage gas compressors and complex chill trains, whichcontribute significantly to the cost of olefin production. If crackedproducts could be produced with minimal or no hydrogen in the reactoreffluent, a significant cost saving could be realized for grassrootsplants and for debottlenecking existing plants, and lower olefinmanufacturing cost could be realized.

[0010] Conventional approaches to deal with the hydrogen issue havefocused on post-reactor separation. That is, attempts have been made touse various reaction and/or separation techniques such as pressure swingadsorption or membranes to remove hydrogen from the olefins. However,these technologies suffer from a few disadvantages. First, they mostlyoperate at relatively high pressure (greater than about 700 kPa), whichdoes not help reduce the burden on the compressors. Second, thesetechnologies are expensive. Third, their performance of separating theolefin product into a H₂-rich stream and a H₂-poor stream is oftenunsatisfactory. A typical problem has been the loss of olefins to thehydrogen-rich stream due to an incomplete separation. As a result, manycommercial plants still employ the complex and costly high-pressurecryogenic separation.

[0011] U.S. Pat. No. 4,497,971, which is incorporated herein byreference in its entirety, relates to an improved catalytic process forthe cracking and oxidative dehydrogenation of light paraffins, and acatalyst therefor. According to this patent, a paraffin or mixture ofparaffins having from 2 to 5 carbon atoms is oxidatively dehydrogenatedin the presence of a cobalt-based catalyst composition which not onlyhas oxidative dehydrogenation capabilities but also has the capabilityto crack paraffins having more than two carbon atoms so that a paraffinsuch as propane can be converted to ethylene. If the feed to theoxidative dehydrogenation process contains paraffins having more thantwo carbon atoms, some cracking of such paraffins will occur at theconditions at which the oxidative dehydrogenation process is carriedout.

[0012] U.S. Pat. No. 4,781,816, which is incorporated herein byreference in its entirety, relates to a catalytic cracking process andto a process for cracking heavy oils. It is an object of the disclosedinvention to provide a process for cracking hydrocarbon-containingfeedstocks, which contain vanadium compounds as impurities. According tothis patent, the feedstream to be treated contains at least about 5 wppmvanadium. The catalyst comprises a physical mixture of zeolite embeddedin an inorganic refractory matrix material, and at least one oxide of ametal selected from the group consisting of Be, Mg, Ca, Sr, Ba, and La(preferably MgO) on a support material comprising silica.

[0013] U.S. Pat. No. 5,002,653, which is incorporated herein byreference in its entirety, relates to an improved catalytic crackingprocess using a catalyst composition for use in the conversion ofhydrocarbons to lower-boiling fractions. More particularly, theinvention comprises a process for using a dual component catalyst systemfor fluid catalytic cracking, which catalyst demonstrates vanadiumpassivation and improved sulfur tolerance. The catalyst comprises afirst component comprising a cracking catalyst having high activity,and, a second component, as a separate and distinct entity, the secondcomponent comprising a calcium/magnesium-containing material incombination with a magnesium-containing material, wherein thecalcium/magnesium-containing compound is active for metals trapping,especially vanadium trapping.

[0014] U.S. Pat. No. 5,527,979, which is incorporated herein byreference in its entirety, relates to a catalytic oxidativedehydrogenation process for alkane molecules having 2 to 5 carbon atoms.It is an object of the disclosed invention to provide a process fordehydrogenation of alkanes to alkenes. More particularly, the inventioncomprises a process of at least two reactors in series, in which analkane feed is dehydrogenated to produce alkenes and hydrogen over anequilibrium dehydrogenation catalyst in a first reactor, and theeffluent from the first reactor, along with oxygen, is passed into asecond reactor containing a metal oxide catalyst which serves toselectively catalyze the combustion of hydrogen. At least a portion ofthe effluent from the second reactor is contacted with a solid materialcomprising a dehydrogenation catalyst to further convert unreactedalkanes to additional quantities of alkenes and hydrogen. Theequilibrium dehydrogenation catalyst comprises at least one metal fromCr, Mo, Ga, Zn and a metal from Groups 8-10. The metal oxide catalystcomprises an oxide of at least one metal from the group of Bi, In, Sb,Zn, Tl, Pb, and Te.

[0015] U.S. Pat. No. 5,530,171, which is incorporated herein byreference in its entirety, relates to a catalytic oxidativedehydrogenation process for alkane molecules having 2 to 5 carbon atoms.It is an object of the disclosed invention to provide a process fordehydrogenation of alkanes to alkenes. More particularly, the inventioncomprises a process of simultaneous equilibrium dehydrogenation ofalkanes to alkenes and combustion of the hydrogen formed to drive theequilibrium dehydrogenation reaction further to the product alkenes. Theprocess involves passing the alkane feed into a reactor containing bothan equilibrium dehydrogenation catalyst and a reducible metal oxide,whereby the alkane is dehydrogenated and the hydrogen produced issimultaneously and selectively combusted in oxidation/reduction reactionwith the reducible metal oxide. The process further comprisesinterrupting the flow of alkane into the reaction zone, reacting thereduced metal oxide with a source of oxygen to regenerate the originaloxidized form of the reducible metal oxide, and resuming the reaction inthe reaction zone using the regenerated from of the reducible metaloxide. The dehydrogenation catalyst comprises Pt or Pd, and thereducible metal oxide is an oxide of at least one metal from the groupof Bi, In, Sb, Zn, Tl, Pb, and Te.

[0016] U.S. Pat. No. 5,550,309, which is incorporated herein byreference in its entirety, relates to a catalytic dehydrogenationprocess for a hydrocarbon or oxygenated hydrocarbon feed. Moreparticularly, the invention comprises a process of contacting the feedwith a catalyst bed comprising a dehydrogenation catalyst and a porouscoated hydrogen retention agent in which the dehydrogenation catalystproduces a product stream of a dehydrogenated product and hydrogen andthe porous coated hydrogen retention agent selectively removes, adsorbs,or reacts with some of the hydrogen from the product stream, removingthe reaction products from the reaction chamber, removing the adsorbedhydrogen from the hydrogen retention agent, or oxidizing the reducedhydrogen retention agent to regenerate the hydrogen retention agent, andusing the regenerated hydrogen retention agent for reaction with feed.

[0017] U.S. Pat. No. 4,466,884, which is incorporated herein byreference in its entirety, relates to a catalytic cracking process forfeedstocks having high metals content such as vanadium, nickel, iron andcopper. More particularly, the invention comprises a process ofcontacting the feed with a catalyst composition comprising a solidcracking catalyst and a diluent containing antimony and/or tin. Thesolid cracking catalyst is to provide good cracking activity. Thediluent can be compound or compounds having little activity such asmagnesium compounds or titanium compounds. The function of the antimonyand/or tin in the diluent is to react with the nickel or vanadium in thefeedstocks to form inert compounds thereby reducing the deactivatingeffects of nickel and vanadium on the solid cracking catalyst.

[0018] U.S. Pat. No. 4,451,355, which is incorporated herein byreference in its entirety, relates to a hydrocarbon conversion processfor feedstocks having a significant concentration of vanadium. Moreparticularly, the invention comprises a process of contacting the feedhaving a significant concentration of vanadium with a cracking catalystcontaining a calcium containing additive selected from the groupconsisting of calcium-titanium, calcium-zirconium,calcium-titanium-zirconium oxides, and mixtures thereof. A preferredcalcium additive is a calcium titanate perovskite (CaTiO3) or calciumzirconate (CaZrO3) perovskite. It is theorized that addition of thecalcium-containing additive prevents the detrimental vanadiuminteraction with the zeolite in the cracking catalyst by acting as asink for vanadium.

[0019] Emission of NO_(x) from fluid catalytic cracking (FCC)regenerator is increasingly controlled by various state and localregulations. Current FCC regenerator flue gas contains significantNO_(x) emissions (typically, in the range of 100-500 ppm), along withother pollutants, e.g., CO and SO_(x). NO_(x) emissions in theregenerator flue gas arise primarily from the oxidation ofnitrogen-containing compounds deposited on the base cracking catalyst ascoke. Nearly 40% of the nitrogen in the hydrocarbon feed is present ascoke on the base catalyst before it enters the regenerator. Of this,roughly 10% of the nitrogen is oxidized to NO and released in theregenerator flue gas, while the remaining is reduced to N₂. Therefore,substantial NO_(x) emissions can result from processing ofhigh-nitrogen, gas oil feeds.

[0020] Conventional approaches to deal with NO_(x) emissions in FCCregenerator flue gas have focused on post-reactor, selective catalyticreduction (SCR) of NO by NH₃. However, there are significant capital andoperating costs associated with implementing SCR technology. Morerecently, de-NO_(x) additives have been designed in a way that they donot affect the catalytic cracking reactions or product yields in theriser, while reducing NO_(x) by CO present in the regenerator. Theefficacy of these de-NO_(x) additives depends greatly on COconcentration present during regeneration. Full-burn regeneratorsutilizing CO promoters to help oxidize CO to CO₂ have significantlylower CO concentration, thereby affecting the de-NO_(x) performance ofthese additives.

[0021] A significant need exists for a cracking technology thatovercomes the previously discussed disadvantages of present, commercialcracking technology due to of the presence of hydrogen in crackedproducts. Additionally, there is a need for a technology which canreduce the NO_(x) emissions resulting from the regeneration of catalystsused in cracking.

SUMMARY OF THE INVENTION

[0022] The present invention relates to a catalyst system for reducingthe hydrogen content of the effluent from a cracking reactor. Thecatalyst system comprises (1) at least one solid acid component and (2)at least one metal-based component, said metal-based componentconsisting essentially of (a) a metal combination selected from thegroup consisting of:

[0023] i) at least one metal from Group 3 and at least one metal fromGroups 4-15 of the Periodic Table of the Elements;

[0024] ii) at least one metal from Groups 5-15 of the Periodic Table ofthe Elements, and at least one metal from at least one of Groups 1, 2,and 4 of the Periodic Table of the Elements;

[0025] iii) at least one metal from Groups 1-2, at least one metal fromGroup 3, and at least one metal from Groups 4-15 of the Periodic Tableof the Elements; and

[0026] iv) two or more metals from Groups 4-15 of the Periodic Table ofthe Elements

[0027] and (b) at least one of oxygen and sulfur, wherein the at leastone of oxygen and sulfur is chemically bound both within and between themetals.

[0028] In a further aspect the catalyst system can comprise at least oneof at least one support, at least one filler, and at least one binder.Preferably, the solid acid component and the metal-based component arephysically admixed.

[0029] The solid acid component can comprise at least one of at leastone support, at least one filler and at least one binder. In anotheraspect, the solid acid component can comprise at least one of one ormore amorphous solid acids, one or more crystalline solid acids, and oneor more supported acids. In one embodiment of the present invention, thesolid acid catalyst comprises at least one molecular sieve. In apreferred embodiment, the molecular sieve comprises at least one ofcrystalline silicates, crystalline substituted silicates, crystallinealuminosilicates, crystalline substituted aluminosilicates, crystallinealuminophosphates, crystalline substituted aluminophosphates, and/orzeolite-bound-zeolite, having 8- or greater-than-8 membered oxygen ringsin framework structures. In another embodiment of the present invention,the solid acid component is at least one zeolite. The zeolite cancomprise at least one of faujasite and MFI. The faujasite zeolite can beY zeolite or modified Y zeolites such as, for example, dealuminated Yzeolite, high silica Y zeolite, or rare earth-exchanged Y zeolite. TheMFI zeolite can be ZSM-5 zeolite or modified ZSM-5 zeolites such asphosphorous treated ZSM-5 zeolite and lanthanum treated ZSM-5 zeolite.In another embodiment of the present invention, the solid acid componentcan also be conventional FCC catalysts including catalysts containingzeolite Y, modified zeolite Y, Zeolite beta, and mixtures thereof, andcatalysts containing a mixture of zeolite Y and a medium-pore,shape-selective molecular sieve species such as ZSM-5, or a mixture ofan amorphous acidic material and ZSM-5. Such catalysts are described inU.S. Pat. No. 5,318,692, incorporated by reference herein.

[0030] In a further embodiment of the present invention, the metal-basedcomponent comprises at least one perovskite, spinel, or birnessitecrystal structure. Furthermore, the metal-based component can compriseat least one of at least one support, at least one filler and at leastone binder.

[0031] In one embodiment of the present invention, the metal-basedcomponent is a combination of oxygen and/or sulfur with one or moremetals from Group 3 and one or more metals from Groups 4-15 of thePeriodic Table of the Elements (hereinafter “sub-group 1”). Withinsub-group 1, the preferred metals from Group 3 are at least one ofscandium, yttrium, lanthanum, cerium, samarium, ytterbium andpraseodymium; and the preferred metals from Groups 4-15 are titanium,zirconium, niobium, molybdenum, tungsten, manganese, iron, cobalt,iridium, nickel, palladium, platinum, copper, zinc, aluminum gallium,indium, germanium, tin, antimony, and bismuth.

[0032] In an alternative embodiment of the present invention, themetal-based component is a combination of oxygen and/or sulfur with oneor more metals from Groups 5-15 of the Periodic Table of the Elementsand one or more metals from at least one of Groups 1, 2, and/or Group 4of the Periodic Table of the Elements (hereinafter “sub-group 2”).Within sub-group 2, the preferred metals from Groups 5-15 are at leastone of niobium, molybdenum, tungsten, manganese, iron, cobalt, iridium,nickel, palladium, platinum, copper, zinc, aluminum gallium, indium,germanium, tin, antimony, and bismuth; the preferred metals from Groups1 and 2 are sodium, potassium magnesium, calcium, strontium, and barium;and the preferred metals from Group 4 are titanium and zirconium.

[0033] In another alternative embodiment of the present invention, themetal-based component is a combination of oxygen and/or sulfur with oneor more metals from Groups 1 and 2, one or more metals from Group 3, andone or more metals from Groups 4-15 of the Periodic Table of theElements (hereinafter “sub-group 3”). Within sub-group 3, the preferredmetals from Groups 1 and 2 are at least one of sodium, potassium,magnesium, calcium, strontium and barium; the preferred metals fromGroup 3 are at least one of scandium, yttrium, lanthanum, cerium,samarium, ytterbium and praseodymium; and the preferred metals fromGroups 4-15 are at least one of titanium, zirconium, niobium,molybdenum, tungsten, manganese, iron, cobalt, iridium, nickel,palladium, platinum, copper, zinc, aluminum gallium, indium, germanium,tin, antimony, and bismuth.

[0034] In yet another embodiment of the present invention, themetal-based component is a combination of oxygen and/or sulfur with twoor more metals from Groups 4-15 of the Periodic Table of the Elements(hereinafter “sub-group 4”). Within sub-group 4, the preferred metalsfrom Groups 4-15 are at least two of titanium, zirconium, niobium,molybdenum, tungsten, manganese, iron, cobalt, iridium, nickel,palladium, platinum, copper, zinc, aluminum gallium, indium, germanium,tin, antimony, and bismuth.

[0035] According to another aspect of the present invention, a processcomprises simultaneously contacting a hydrocarbon feedstream undercracking conditions with both a cracking catalyst and a selectivehydrogen combustion catalyst in a catalyst system comprising (1) atleast one cracking catalyst comprising at least one solid acid componentand (2) at least one metal-based component which consists of (a) atleast one of oxygen and sulfur and (b) a metal combination selected fromthe group consisting of:

[0036] i) at least one metal from Group 3 and at least one metal fromGroups 4-15 of the Periodic Table of the Elements;

[0037] ii) at least one metal from Groups 5-15 of the Periodic Table ofthe Elements, and at least one metal from at least one of Groups 1, 2,and 4 of the Periodic Table of the Elements;

[0038] iii) at least one metal from Groups 1 and 2, at least one metalfrom Group 3, and at least one metal from Groups 4-15 of the PeriodicTable of the Elements; and

[0039] iv) two or more metals from Groups 4-15 of the Periodic Table ofthe Elements,

[0040] wherein the at least one of oxygen and sulfur is chemically boundboth within and between the metals.

[0041] Preferably, the yield of hydrogen is less than the yield ofhydrogen when contacting said hydrocarbon feedstream(s) with said solidacid component alone under said catalytic reaction conditions.

[0042] In a further aspect of the present invention, a catalyticcracking process comprises:

[0043] (A) charging at least one hydrocarbon feedstream to a fluidcatalytic cracking reactor,

[0044] (B) charging a hot fluidized cracking/selective hydrogencombustion catalyst system from a catalyst regenerator to said fluidcatalytic cracking reactor, said catalyst system comprising: (1) atleast one cracking catalyst comprising at least one solid acid componentand(2) at least one metal-based component consisting essentially of (a)a metal combination selected from the group consisting of:

[0045] i) at least one metal from Group 3 and at least one metal fromGroups 4-15 of the Periodic Table of the Elements;

[0046] ii) at least one metal from Groups 5-15 of the Periodic Table ofthe Elements, and at least one metal from at least one of Groups 1, 2,and 4 of the Periodic Table of the Elements;

[0047] iii) at least one metal from Groups 1-2, at least one metal fromGroup 3, and at least one metal from Groups 4-15 of the Periodic Tableof the Elements; and

[0048] iv) two or more metals from Groups 4-15 of the Periodic Table ofthe Elements

[0049]  and (b) at least one of oxygen and sulfur, wherein the at leastone of oxygen and sulfur is chemically bound both within and between themetals,

[0050] (C) catalytically cracking said feedstream(s) and combustingresultant hydrogen at about 300 to about 800° C. to produce a stream ofcracked products and uncracked feed and a spent catalyst systemcomprising said fluid catalytic cracking catalyst and said selectivehydrogen combustion catalyst which are discharged from said reactor,

[0051] (D) separating a phase rich in said cracked products anduncracked feed from a phase rich in said spent catalyst system,stripping said spent catalyst system at stripping conditions to producea stripped catalyst phase,

[0052] (E) decoking and oxidizing said stripped catalyst phase in acatalyst regenerator at catalyst regeneration conditions to produce saidhot fluidized cracking/selective hydrogen combustion catalyst system,which is recycled to the said reactor, and

[0053] (F) separating and recovering said cracked products and uncrackedfeed.

[0054] Another aspect of the present invention relates to a processcomprising contacting at least one hydrocarbon feedstream with acracking/selective hydrogen combustion catalyst system under effectivecatalytic reaction conditions to produce cracked products and uncrackedfeed comprising liquid and gaseous hydrocarbons, wherein the yield ofhydrogen is less than the yield of hydrogen when contacting saidhydrocarbon feedstream(s) with said cracking catalyst alone under saidcatalytic reaction conditions.

BRIEF DESCRIPTION OF THE DRAWINGS

[0055]FIG. 1 is a plot showing the NO_(x) reduction properties of thecatalyst system described herein.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

[0056] Unless otherwise stated, all percentages, parts, ratios, and thelike are by weight.

[0057] Unless otherwise stated, certain terms used herein shall have thefollowing meaning.

[0058] The term “paraffins” shall mean compounds having no carbon-carbondouble bonds and either the formula C_(n)H_(2n+2) or C_(n)H_(2n), wheren is an integer.

[0059] The term “naphthenes” shall mean compounds having nocarbon-carbon double bonds and the formula C_(n)H_(2n), where n is aninteger.

[0060] The term “paraffinic feedstream” shall mean a hydrocarbonfeedstream containing some amount of paraffins but no olefins.

[0061] The term “olefins” shall mean non-aromatic hydrocarbons havingone or more carbon-carbon double bonds.

[0062] The term “light olefins” shall mean ethylene, propylene, andbutylenes.

[0063] The term “light paraffins” shall mean methane, ethane, propane,and butanes.

[0064] The term “catalyst to oil ratio” shall mean the relative amountof catalyst to hydrocarbon by weight.

[0065] The term “aromatics” shall mean compounds having one or more thanone benzene ring.

[0066] The term “physical admixture” shall mean a combination of two ormore components obtained by mechanical (i.e., non-chemical) means.

[0067] The term “chemically bound” shall mean bound via atom to atombonds.

[0068] The term “cracking/selective hydrogen combustion” shall mean bothcracking reaction and selective hydrogen combustion reaction.

[0069] The term “cracking catalyst” shall broadly mean a catalyst orcatalysts capable of promoting cracking reactions whether used as basecatalyst(s) and/or additive catalyst(s).

[0070] The term “selective hydrogen combustion catalyst” shall broadlymean a material or materials capable of promoting or participating in aselective hydrogen combustion reaction, using either free oxygen orlattice oxygen contained in the selective hydrogen combustion catalyst.

[0071] The term “cracking/selective hydrogen combustion catalyst” shallmean 1) a catalyst system comprised of a physical admixture of one ormore cracking catalysts and one or more selective hydrogen combustioncatalysts or 2) one or more selective hydrogen combustion catalystschemically bound to one or more cracking catalysts.

[0072] The term “cracking” shall mean the reactions comprising breakingof carbon-carbon bonds and carbon-hydrogen bonds of at least some feedmolecules and the formation of product molecules that have no carbonatom and/or fewer carbon atoms than that of the feed molecules.

[0073] The term “Group 3 metals” shall mean elements having atomicnumbers of 21, 39, 57 through 71, and 89 through 92.

[0074] The term “selective hydrogen combustion” shall mean reactinghydrogen with oxygen to form water or steam without substantiallyreacting hydrocarbons with oxygen to form carbon monoxide, carbondioxide, and/or oxygenated hydrocarbons.

[0075] The term “yield” shall mean weight of a product produced per unitweight of feed, expressed in terms of weight %.

[0076] Unless otherwise stated, a reference to an element, metal,compound, or component includes the element, metal, compound, orcomponent by itself, as well as in combination with other elements,metal, compounds, or components, such as mixtures of compounds.

[0077] Further, when an amount, concentration, or other value orparameter is given as a list of upper preferable values and lowerpreferable values, this is to be understood as specifically disclosingall ranges formed from any pair of an upper preferred value and a lowerpreferred value, regardless of whether ranges are separately disclosed.

[0078] The particulars shown herein are by way of example and forpurposes of illustrative discussion of the embodiments of the presentinvention only and are presented in the cause of providing what isbelieved to be the most useful and readily understood description of theprinciples and conceptual aspects of the present invention. In thisregard, no attempt is made to show structural details of the presentinvention in more detail than is necessary for the fundamentalunderstanding of the present invention, the description making apparentto those skilled in the art how the several forms of the presentinvention may be embodied in practice.

[0079] Hydrocarbon Feedstream

[0080] The present invention relates to a catalyst system for treating ahydrocarbon feedstream. Such a feedstream could comprise, by way ofnon-limiting example, hydrocarbonaceous oils boiling in the range ofabout 221° C. to about 566° C., such as gas oil, steam cracked gas oil,and residues; heavy hydrocarbonaceous oils comprising materials boilingabove about 566° C.; heavy and reduced petroleum crude oil; petroleumatmospheric distillation bottoms; petroleum vacuum distillation bottoms;heating oil; pitch; asphalt; bitumen; other heavy hydrocarbon residues;tar sand oils; shale oil; liquid products derived from coal liquefactionprocesses; and mixtures thereof. Other possible feedstreams couldcomprise steam heating oil, jet fuel, diesel, kerosene, gasoline, cokernaphtha, steam cracked naphtha, catalytically cracked naphtha,hydrocrackate, reformate, raffinate reformate, Fischer-Tropsch liquids,Fischer-Tropsch gases, natural gasoline, distillate, virgin naphtha, C₅₊olefins (i.e., C₅ olefins and above), C₅₊ paraffins, ethane, propane,butanes, butenes, and butadiene. The present invention is also usefulfor catalytically cracking olefinic and paraffinic feedstreams.Non-limiting examples of olefinic feedstreams are cat-cracked naptha,coker naptha, steam cracked gas oil, and olefinic Fischer-Tropschliquids. Non-limiting examples of paraffinic feedstreams are virginnaptha, natural gasoline, reformate, and raffinate. Preferably, thehydrocarbon feedstream comprises at least one of paraffins, olefins,aromatics, naphthenes, and mixtures thereof, which produces lightolefins, hydrogen, light paraffins, gasoline, and optionally, crackednaphtha, cracked gas oil, tar, and/or coke. Typically, the crackedproducts from processes in accordance with the present inventioncomprise hydrogen, light olefins, light paraffins, and olefins andparaffins having more than four carbon atoms. Products can be liquidand/or gaseous.

[0081] Catalyst System

[0082] The catalyst system of the present invention comprises (1) atleast one solid acid component and (2) at least one metal-basedcomponent, said metal-based component consisting essentially of (a) ametal combination selected from the group consisting of:

[0083] i) at least one metal from Group 3 and at least one metal fromGroups 4-15 of the Periodic Table of the Elements;

[0084] ii) at least one metal from Groups 5-15 of the Periodic Table ofthe Elements, and at least one metal from at least one of Groups 1, 2,and 4 of the Periodic Table of the Elements;

[0085] iii) at least one metal from Groups 1-2, at least one metal fromGroup 3, and at least one metal from Groups 4-15 of the Periodic Tableof the Elements; and

[0086] iv) two or more metals from Groups 4-15 of the Periodic Table ofthe Elements

[0087] and (b) at least one of oxygen and sulfur, wherein the at leastone of oxygen and sulfur is chemically bound both within and between themetals.

[0088] Preferably the solid acid component is a cracking catalyst andthe metal-based component is a selective hydrogen combustion catalyst.

[0089] The solid acid catalyst can be in physical admixture with, orchemically bound to, the metal-based component. The metals selected fromcombinations (i), (ii), (iii), or (iv) can be chemically bound, bothbetween and within the Groups specified. For example, within combination(ii), it would be within the scope of the present invention for two ormore metals from Groups 1 and 2 to be chemically bound to each other aswell as chemically bound to the metal(s) from Groups 5-15.Alternatively, the chemical binding can be only between metals ofdifferent groups and not between metals within the same group, i.e., twoor more metals from Groups 1 and 2 being in admixture with each otherbut chemically bound to the metal(s) from Groups 5-15.

[0090] Solid Acid

[0091] The solid acid component is described by the Br{acute over(ø)}nsted and Lewis definitions of any material capable of donating aproton or accepting an electron pair. This description can be found inK. Tanabe. Solid Acids and Bases: their catalytic properties. Tokyo:Kodansha Scientific, 1970, p. 1-2. This reference is incorporated hereinby reference in its entirety. The solid acid component can comprise atleast one of a solid acid, a supported acid, or a mixture thereof. Thesolid acid component can comprise nonporous, microporous, mesoporous,macroporous solids or a mixture thereof. These porosity designations areIUPAC conventions and are defined in K. S. W. Sing, D. H. Everett, R. A.W. Haul L. Moscou, R. A. Pierotti, J. Rouquérol, T. Siemieniewska,Pure&Appl. Chem. 1995, 57(4), pp. 603-619, which is incorporated hereinby reference in its entirety.

[0092] Non-limiting examples of solid acid components are natural clayssuch as kaolinite, bentonite, attapulgite, montmorillonite, clarit,fuller's earth, cation exchange resins and SiO₂.Al₂O₃, B₂O₃.Al₂O₃,Cr₂O₃.Al₂O₃, MoO₃.Al₂O₃, ZrO₂.SiO₂, Ga₂O₃.SiO₂, BeO.SiO₂, MgO.SiO₂,CaO.SiO₂, SrO.SiO₂, Y₂O₃.SiO₂, La₂O₃.SiO₂, SnO.SiO₂, PbO.SiO₂, MoO₃.Fe₂(MoO₄)₃, MgO.B₂O₃, TiO₂.ZnO, ZnO, Al₂O₃, TiO₂, CeO₂, As₂O₃, V₂O₅, SiO₂,Cr₂O₃, MoO₃, ZnS, CaS, CaSO₄, MnSO₄, NiSO₄, CuSO₄, CoSO₄, CdSO₄, SrSO₄,ZnSO₄, MgSO₄, FeSO₄, BaSO₄, KHSO₄, K₂SO₄, (NH₄)₂SO₄, Al₂(SO₄)₃,Fe₂(SO₄)₃, Cr₂(SO₄)₃, Ca(NO₃)₂, Bi(NO₃), Zn(NO₃)₂, Fe(NO₃)₃, CaCO₃,BPO₄, FePO₄,CrPO₄, Ti₃(PO₄)₄, Zr₃(PO₄)₄, Cu₃(PO₄)₂, Ni₃(PO₄)₂, AlPO₄,Zn₃(PO₄)₂, Mg₃(PO₄)₂, AlCl₃, TiCl₃, CaCl₂, AgCl₂, CuCl, SnCl₂, CaF₂,BaF₂, AgClO₄, and Mg(ClO₄)₂. Depending on the synthesis conditions,these materials can be prepared as nonporous, microporous, mesoporous,or macroporous solids, as defined in the reference cited above.Conditions necessary to these preparations are known to those ofordinary skill in the art.

[0093] Non-limiting examples of solid acids can also include bothnatural and synthetic molecular sieves. Molecular sieves havesilicate-based structures (“zeolites”) and AIPO-based structures. Somezeolites are silicate-based materials which are comprised of a silicalattice and, optionally, alumina combined with exchangeable cations suchas alkali or alkaline earth metal ions. For example, faujasites,mordenites, and pentasils are non-limiting illustrative examples of suchsilicate-based zeolites. These types of zeolites have 8-, 10-, or12-membered ring zeolites, such as Y, beta, ZSM-5, ZSM-22, ZSM-48, andZSM-57.

[0094] Other silicate-based materials suitable for use in practicing thepresent invention include zeolite bound zeolites as described in WO97/45387, incorporated herein by reference in its entirety. Thesematerials comprise first crystals of an acidic intermediate pore sizefirst zeolite and a binder comprising second crystals of a secondzeolite. Unlike zeolites bound with amorphous material such as silica oralumina to enhance the mechanical strength of the zeolite, the zeolitebound zeolite catalyst does not contain significant amounts ofnon-zeolitic binders.

[0095] The first zeolite used in the zeolite bound zeolite catalyst isan intermediate pore size zeolite. Intermediate pore size zeolites havea pore size of from about 5 to about 7 Å and include, for example, AEL,MFI, MEL, MFS, MEI, MTW, EUO, MTT, HEU, FER, and TON structure typezeolites. These zeolites are described in Atlas of Zeolite StructureTypes, eds. W. H. Meier and D. H. Olson, Butterworth-Heineman, ThirdEdition, 1992, which is incorporated herein by reference in itsentirety. Non-limiting, illustrative examples of specific intermediatepore size zeolites are ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-34,ZSM-35, ZSM-38, ZSM-48, ZSM-50 AND ZSM-57. Preferred first zeolites aregalliumsilicate zeolites having an MFI structure and aluminosilicatezeolites having an MFR structure.

[0096] The second zeolite used in the zeolite bound zeolite structurewill usually have an intermediate pore size, preferably about 5.0 toabout 5.5 Å, and have less activity than the first zeolite. Preferably,the second zeolite will be substantially non-acidic and will have thesame structure type as the first zeolite. The preferred second zeolitesare aluminosilicate zeolites having a silica to alumina mole ratiogreater than 100 such as low acidity ZSM-5. If the second zeolite is analuminosilicate zeolite, the second zeolite will generally have a silicato alumina mole ratio greater than 100:1, e.g., 500:1; 1,000:1, or more,and in some applications will contain no more than trace amounts ofalumina. The second zeolite can also be silicalite, i.e., an MFI typesubstantially free of alumina, or silicalite 2, an MEL typesubstantially free of alumina. The second zeolite is usually present inthe zeolite bound zeolite catalyst in an amount in the range of fromabout 10% to about 60% by weight based on the weight of the firstzeolite and, more preferably, from about 20% to about 50% by weight.

[0097] The second zeolite crystals preferably have a smaller size thanthe first zeolite crystals and more preferably will have an averageparticle size from about 0.1 to about 0.5 microns. The second zeolitecrystals, in addition to binding the first zeolite particles andmaximizing the performance of the catalyst, will preferably intergrowand form an overgrowth which coats or partially coats the first zeolitecrystals. Preferably, the crystals will be resistant to attrition.

[0098] The zeolite bound zeolite catalyst is preferably prepared by athree-step procedure. The first step involves the synthesis of the firstzeolite crystals prior to converting it to the zeolite bound zeolitecatalyst. Next, a silica-bound aluminosilicate zeolite can be prepared,preferably by mixing a mixture comprising the aluminosilicate crystals,a silica gel or sol, water and, optionally, an extrusion aid and,optionally, a metal component until a homogeneous composition in theform of an extrudable paste develops. The final step is the conversionof the silica present in the silica-bound catalyst to a second zeolitewhich serves to bind the first zeolite crystals together.

[0099] It is to be understood that the above description of zeolitebound zeolites can be equally applied to non-zeolitic molecular sieves(i.e., AIPO's).

[0100] Other molecular sieve materials suitable for this inventioninclude aluminophosphate-based materials. Aluminophosphate-based (AlPO)materials are made of alternating AlO₄ and PO₄ tetrahedra. Members ofthis family have 8- (e.g., AlPO-12, -17, -21, -25, -34, -42), 10-(e.g.,AlPO-11, 41.), or 12- (AlPO-5, -31) membered oxygen ring channels.Although AlPO₄s are neutral, substitution of Al and/or P by cations withlower charge introduces a negative charge in the framework, which iscountered by cations imparting acidity.

[0101] Substitution of silicon for P and/or a P—Al pair turns theneutral binary composition (i.e., Al, P) into a series ofacidic-ternary-composition (Si, Al, P) based SAPO materials, such asSAPO-5, -11, -14, -17, -18, -20, -31, -34, -41, and -46. Acidic ternarycompositions can also be created by substituting divalent metal ions foraluminum, generating the MeAPO materials. Me is a metal ion which can beselected from the group consisting of, but not limited to, Mg, Co, Fe,Zn and the like. Acidic materials such as MgAPO (magnesium substituted),CoAPO (cobalt substituted), FeAPO (iron substituted), MnAPO (manganesesubstituted) ZnAPO (zinc substituted) and others belong to thiscategory. Substitution can also create acidic quaternary-compositionbased materials such as the MeAPSO series, including FeAPSO (Fe, Al, P,and Si), MgAPSO (Mg, Al, P, Si), MnAPSO, CoAPSO, ZnAPSO, and more. Othersubstituted aluminophosphate-based materials include ElAPO and ElAPSO(where El=B, As, Be, Ga, Ge, Li, Ti, and others). As mentioned above,these materials have the appropriate acidic strength for reactions suchas cracking. The more preferred aluminophosphate-based materials include10- and 12-membered ring materials (for example, SAPO-11, SAPO-31,SAPO-41; MeAPO-11, MeAPO-31, MeAPO-41; MeAPSO-11, MeAPSO-31, MeAPSO-41;ElAPO-11, ElAPO-31, ElAPO-41; ElAPSO-11, ElAPSO-31, ElAPSO-41) whichhave significant olefin selectivity due to their channel structure.

[0102] Supported acid materials are either crystalline or amorphousmaterials, which may or may not be themselves acidic, modified toincrease the acid sites on the surface. Non-limiting, illustrativeexamples are H₂SO₄, H₃PO₄, H₃BO₃, or CH₂(COOH)₂, mounted on silica,quartz, sand, alumina, or diatomaceous earth., as well asheteropolyacids mounted on silica, quartz, sand, alumina, ordiatomaceous earth. Non-limiting, illustrative examples of crystallinesupported acid materials are acid-treated molecular sieves, sulfatedzirconia, tungstated zirconia, phosphated zirconia, and phosphatedniobia.

[0103] Although the term “zeolites” includes materials containing silicaand optionally, alumina, it is recognized that the silica and aluminaportions may be replaced in whole or in part with other oxides. Forexample, germanium oxide, tin oxide, phosphorus oxide, and mixturesthereof can replace the silica portion. Boron oxide, iron oxide, galliumoxide, indium oxide, and mixtures thereof can replace the aluminaportion. Accordingly, “zeolite” as used herein, shall mean not onlymaterials containing silicon and, optionally, aluminum atoms in thecrystalline lattice structure thereof, but also materials which containsuitable replacement atoms for such silicon and aluminum, such asgallosilicates, borosilicates, ferrosilicates, and the like.

[0104] Mesoporous solid acids can be ordered and non-ordered.Non-limiting examples of ordered mesoporous materials include pillaredlayered clays (PILC's) such as MCM-41 and MCM-48. Non-limiting examplesof non-ordered mesoporous materials include silica and titania-basedxerogels and aerogels.

[0105] The solid acid component can also be a conventional FCC catalystincluding catalysts containing large-pore zeolite Y, modified zeolite Y,zeolite beta, and mixtures thereof, and catalysts containing a mixtureof zeolite Y or modified zeolite Y and a medium-pore, shape-selectivemolecular sieve species such as ZSM-5 or modified ZSM-5, or a mixture ofan amorphous acidic material and ZSM-5 or modified ZSM-5. Such catalystsare described in U.S. Pat. No. 5,318,692, incorporated by referenceherein. The zeolite portion of the FCC catalyst particle will typicallycontain from about 5 wt. % to 95 wt. % zeolite-Y (or alternatively theamorphous acidic material) with the balance of the zeolite portion beingZSM-5. Useful medium-pore, shape-selective molecular sieves includezeolites such as ZSM-5, which is described in U.S. Pat. Nos. 3,702,886and 3,770,614; ZSM-11 described in U.S. Pat. No. 3,709,979; ZSM-12 inU.S. Pat. No. 3,832,449; ZSM-21 and ZSM-38 in U.S. Pat. No. 3,948,758;ZSM-23 in U.S. Pat. No. 4,076,842; and ZSM-35 in U.S. Pat. No,4,016,245. All of the above patents are incorporated herein byreference.

[0106] The large pore and shape selective zeolites may include“crystalline admixtures” which are thought to be the result of faultsoccurring within the crystal or crystalline area during the synthesis ofthe zeolites. Examples of crystalline admixtures of ZSM-5 and ZSM-11 aredisclosed in U.S. Pat. No. 4,229,424, which is incorporated herein byreference. The crystalline admixtures are themselves medium pore, i.e.,shape selective, size zeolites and are not to be confused with physicaladmixtures of zeolites in which distinct crystals or crystallites ofdifferent zeolites are physically present in the same catalyst compositeor hydrothermal reaction mixtures.

[0107] The conventional FCC catalyst may contain other reactive ornon-reactive components, such as the catalysts described in Europeanpatent EP0600686B1, incorporated by reference herein.

[0108] Metal-Based Component

[0109] The metal-based component consists of (a) at least one of oxygenand sulfur and (b) a metal combination selected from the groupconsisting of:

[0110] i) at least one metal from Group 3 and at least one metal fromGroups 4-15 of the Periodic Table of the Elements;

[0111] ii) at least one metal from Groups 5-15 of the Periodic Table ofthe Elements, and at least one metal from at least one of Groups 1, 2,and 4 of the Periodic Table of the Elements;

[0112] iii) at least one metal from Groups 1 and 2, at least one metalfrom Group 3, and at least one metal from Groups 4-15 of the PeriodicTable of the Elements; and

[0113] iv) two or more metals from Groups 4-15 of the Periodic Table ofthe Elements,

[0114] wherein the at least one of oxygen and sulfur is chemically boundboth within and between the metals. It is intended that reference to ametal from each of the noted Groups would include mixtures of metalsfrom the respective groups. For example, reference to one or more metalsfrom Groups 4-15 includes a mixture of chemically bound metals fromGroups 4 and 15 of the Periodic Table.

[0115] While it is intended that the metal-based component consistessentially of the metals from the combination (sub-group) selectedalong with oxygen and/or sulfur, it is recognized that impurities may bepresent in the manufacturing process and that impurities from thehydrocarbon feedstocks may be adsorbed or incorporated into thecrystalline structure of the metal-based component. To the extent thatsuch impurities do not render the metal-based component ineffective forselective hydrogen combustion they shall be deemed to be within thescope of this invention.

[0116] For the purposes of description of the metal-based component ofthis invention, metals shall be deemed to include all elementsclassified as alkali metals, alkaline earth metals, transition metals,other metals, and metalloids, excluding hydrogen from Group 1; boronfrom Group 13; carbon and silicon from Group 14; and nitrogen,phosphorus, and arsenic from Group 15.

[0117] The preferred metals from Groups 1 and 2 are any of lithium,sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium,strontium, and barium.

[0118] It is noted that rare earth elements are to be included as Group3 metals. Preferably, the metal(s) from Group 3 are any of scandium,yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium,gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium,and lutetium.

[0119] The metal(s) or element(s) from Groups 4-15 can be any metalelement or a mixture of metal elements from Groups 4-15 of the PeriodicTable of the Elements. Preferably, the metal(s) from Groups 4-15 is(are) at least one of titanium, vanadium, chromium, manganese, iron,cobalt, nickel, copper, zinc, aluminum, gallium, germanium, zirconium,niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin,antimony, hafnium, tantalum, tungsten, rhenium, iridium, platinum, gold,lead, and bismuth. More preferably, the metal(s) from Groups 4-15 is(are) at least one of titanium, manganese, iron, cobalt, nickel, copper,zinc, aluminum, gallium, germanium, zirconium, ruthenium, rhodium,palladium, silver, indium, tin, antimony, hafnium, rhenium, iridium,platinum, gold, and bismuth.

[0120] The catalyst can also include at least one of at least onesupport, at least one filler, and at least one binder.

[0121] In one embodiment of the present invention, the metal-basedcomponent is a combination of oxygen and/or sulfur with one or moremetals from Group 3 and one or more metals from Groups 4-15 of thePeriodic Table of the Elements (hereinafter “sub-group 1”). Withinsub-group 1, the preferred metals from Group 3 are at least one ofscandium, yttrium, lanthanum, cerium, samarium, ytterbium andpraseodymium; and the preferred metals from Groups 4-15 are titanium,zirconium, niobium, molybdenum, tungsten, manganese, iron, cobalt,iridium, nickel, palladium, platinum, copper, zinc, aluminum gallium,indium, germanium, tin, antimony, and bismuth. Even more preferredmetal(s) from Group 3 are at least one of scandium, yttrium, lanthanum,and praseodymium; and more preferred metals from Groups 4-15 are one ormore of titanium, zirconium, manganese, iron, cobalt, nickel, copper,zinc, aluminum, indium, and tin.

[0122] Examples of combinations falling within sub-group 1 of the metalcombinations are Y_(a)In_(b)Zn_(c)Mn_(d)O_(x±δ),La_(a)Mn_(b)Ni_(c)Al_(d)O_(x±δ), La_(a)Mn_(b)Al_(c)O_(x±δ),Sc_(a)Cu_(bl)Mn_(c)O_(x±δ), Sc_(a)Zn_(b)Mn_(c)O_(x±δ),La_(a)Zr_(b)O_(x±δ), Mn_(a)Sc_(b)O_(x±δ), and Pr_(a)In_(b)Zn_(c)O_(x±δ),where a, b, c, and d are each between 0 and 1, the sum of a through dequals 1 to 3, x is the sum of a through d plus 1, and δ is the vacancyconcentration or excess oxygen concentration. While oxygen is indicatedin the formulae above, it will be recognized that the positions held byoxygen could be substituted with sulfur.

[0123] In an alternative embodiment of the present invention, themetal-based component is a combination of oxygen and/or sulfur with oneor more metals from Groups 5-15 of the Periodic Table of the Elementsand one or more metals from at least one of Groups 1, 2, and/or Group 4of the Periodic Table of the Elements (hereinafter “sub-group 2”).Within sub-group 2, the preferred metals from Groups 5-15 are at leastone of niobium, molybdenum, tungsten, manganese, iron, cobalt, iridium,nickel, palladium, platinum, copper, zinc, aluminum gallium, indium,germanium, tin, antimony, and bismuth; the preferred metals from Groups1 and 2 are sodium, potassium magnesium, calcium, strontium, and barium;and the preferred metals from Group 4 are titanium and zirconium. Evenmore preferred metals from Groups 5-15 are, manganese, iron, cobalt,nickel, zinc, aluminum, indium, tin, antimony and bismuth.

[0124] Examples of combinations falling within sub-group 2 of the metalcombinations are K_(a)Ba_(b)Mn_(c)O_(x±δ), K_(a)Mg_(b)Mn_(c)O_(x±δ),Na_(a)Mg_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)O_(x±δ),K_(a)Sr_(b)Mn_(c)O_(x±δ), In_(a)Ca_(b)Mn_(c)O_(x±δ),Bi_(a)Ca_(b)Mn_(c)Co_(d)O_(x±δ), Bi_(a)Ca_(b)Mn_(c)Ni_(d)O_(x±δ),Ca_(a)Mn_(b)Sn_(c)Co_(d)O_(x±δ), In_(a)Mg_(b)Mn_(c)Al_(d)O_(x±δ),In_(a)Zn_(b)Mn_(c)Al_(d)O_(x±δ), Na_(a)Ba_(b)Mn_(c)O_(x±δ),Na_(a)Co_(b)Mn_(c)O_(x±δ), Ca_(a)Mn_(b)Sb_(c)O_(x±δ),Ca_(a)Mn_(b)Co_(c)Al_(d)O_(x±δ), Sr_(a)Sb_(b)Sn_(c)Mg_(d)O_(x±δ),K_(a)Co_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)O_(x±δ),Ni_(a)Mg_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)Al_(c)O_(x±δ),Mn_(a)Mg_(b)Ti_(c)O_(x±δ), Sr_(a)Sb_(b)Ca_(c)O_(x±δ),Sr_(a)Ti_(b)Sn_(c)Al_(d)O_(x±δ), Sr_(a)Mn_(b)Ti_(c)Al_(d)O_(x±δ),Ca_(a)Mn_(b)O_(x±δ), Ca_(a)Mn_(b)O_(x±δ), Ca_(a)Zr_(b)Al_(c)O_(x±δ),Bi_(a)Ca_(b)Mn_(c)O_(x±δ), Bi_(a)Sr_(b)Co_(c)Fe_(d)O_(x±δ),Ba_(a)Mn_(b)O_(x±δ), Ca_(a)Mn_(b)Al_(c)O_(x±δ),Ca_(a)Na_(b)Sn_(c)O_(x±δ), and Ba_(a)Zr_(b)O_(x±δ), where a, b, c, and dare each between 0 and 1, the sum of a through d equals 1 to 3, x is thesum of a through d plus 1, and δ is the vacancy concentration or excessoxygen concentration. While oxygen is indicated in the formulae above,it will be recognized that the positions held by oxygen could besubstituted with sulfur.

[0125] In another alternative embodiment of the present invention, themetal-based component is a combination of oxygen and/or sulfur with oneor more metals from Groups 1 and 2, one or more metals from Group 3, andone or more metals from Groups 4-15 of the Periodic Table of theElements (hereinafter “sub-group 3”). Within sub-group 3, the preferredmetals from Groups 1 and 2 are at least one of sodium, potassium,magnesium, calcium, strontium and barium; the preferred metals fromGroup 3 are at least one of scandium, yttrium, lanthanum, cerium,samarium, ytterbium and praseodymium; and the preferred metals fromGroups 4-15 are at least one of titanium, zirconium, niobium,molybdenum, tungsten, manganese, iron, cobalt, iridium, nickel,palladium, platinum, copper, zinc, aluminum gallium, indium, germanium,tin, antimony, and bismuth. Even more preferred metals from Groups 1 and2 are sodium, potassium, calcium, strontium and barium; from Group 3 arescandium, yttrium, and lanthanum; and from Groups 4-15 are titanium,manganese, iron, cobalt, nickel, copper, aluminum, gallium, tin andbismuth.

[0126] Examples of combinations falling within sub-group 3 of the metalcombinations are La_(a)Ca_(b)Mn_(c)Co_(d)Ti_(e)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Sn_(e)O_(x±δ), La_(a)Ca_(b)Co_(c)O_(x±δ),La_(a)Ca_(b)Mn_(c)Ni_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Co_(d)Sn_(e)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Al_(e)O_(x±δ), La_(a)Ca_(b)Mn_(c)Co_(d)O_(x±δ),Ba_(a)K_(b)Bi_(c)La_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Ti_(d)Al_(e)O_(x±δ),La_(a)Ca_(b)Co_(c)Ni_(d)Al_(e)O_(x±δ), La_(a)Ca_(b)Co_(c)Ti_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)O_(x±δ), Ba_(a)Bi_(b)La_(c)O_(x±δ),La_(a)Ca_(b)Mn_(c)Mg_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Fe_(d)O_(x±δ),La_(a)Sr_(b)Co_(c)Al_(d)O_(x±δ), Ba_(a)Bi_(b)Yb_(c)O_(x±δ),Ba_(a)Bi_(b)Sn_(c)La_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Ga_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)Sn_(d)Al_(e)O_(x±δ), La_(a)Ca_(b)Mn_(c)Cu_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Ga_(e)O_(x±67) ,La_(a)Ca_(b)Mn_(c)Al_(d)O_(x±δ), La_(a)Ca_(b)Co_(c)Al_(d)O_(x±δ),Ba_(a)Bi_(b)Sn_(c)La_(d)O_(x±δ), La_(a)Ca_(b)Fe_(c)Co_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Ni_(e)Al_(f)O_(x±δ), Y_(a)Ca_(b)Mn_(c)O_(x±δ),La_(a)Ca_(b)Fe_(c)Co_(d)O_(x±δ), and Sr_(a)Na_(b)Sn_(c)Y_(d)O_(x±δ),where a, b, c, d, e and f are each between 0 and 1, the sum of a throughf equals 1 to 3, x is the sum of a through f plus 1, and δ is thevacancy concentration or excess oxygen concentration. While oxygen isindicated in the formulae above, it will be recognized that thepositions held by oxygen could be substituted with sulfur.

[0127] In yet another embodiment of the present invention, themetal-based component is a combination of oxygen and/or sulfur with twoor more metals from Groups 4-15 of the Periodic Table of the Elements(hereinafter “sub-group 4”). Within sub-group 4, the preferred metalsfrom Groups 4-15 are at least two of titanium, zirconium, niobium,molybdenum, tungsten, manganese, iron, cobalt, iridium, nickel,palladium, platinum, copper, zinc, aluminum gallium, indium, germanium,tin, antimony, and bismuth. Even more preferred are titanium, manganese,cobalt, copper, zinc, aluminum, and indium.

[0128] Examples of combinations falling within sub-group 4 of the metalcombinations are In_(a)Cu_(b)Mn_(c)O_(x±δ), Mn_(a)Co_(b)O_(x±δ),In_(a)Zn_(b)Mn_(c)Al_(d)O_(x±δ), In_(a)Zn_(b)Mn_(c)O_(x±δ),Mn_(a)Zn_(b)O_(x±δ), Mn_(a)Zn_(b)Al_(c)O_(x±δ), In_(a)Mn_(b)O_(x±δ),In_(a)Mn_(b)Al_(c)O_(x±δ), In_(a)Cu_(b)Mn_(c)O_(x±δ), andMn_(a)Zn_(b)Ti_(c)O_(x±δ), where a, b, c, and d are each between 0 and1, the sum of a through d equals 1 to 3, x is the sum of a through dplus 1, and δ is the vacancy concentration or excess oxygenconcentration. While oxygen is indicated in the formulae above, it willbe recognized that the positions held by oxygen could be substitutedwith sulfur.

[0129] The remaining component of the metal-based component inaccordance with the invention is at least one of sulfur and oxygen.Oxygen is preferred. It is noted that at least a portion of the sulfurpresent in a metal-based component could be removed in the SHC reactionand replaced by oxygen in the regeneration process. It is also notedthat in embodiments in which the hydrocarbon feed contained sulfurcompounds, the metal-based component could have sulfur present in thestructure. Therefore, it is likely that applications of this inventionwith sulfur-containing feedstock could involve a metal-based componentcontaining both sulfur and oxygen regardless of which is used in theinitial formulation of the metal-based component.

[0130] In a preferred embodiment the metal-based component can adopt aperovskite (ABO₃) crystal structure, a spinel (AB₂O₄) crystal structure,or a birnessite (A_(z)BO_(x)) crystal structure, where A and B are twodistinct metal sites.

[0131] In an embodiment with a perovskite crystal structure, each metalsite can comprise one or more metal cations. The crystal structure canbe significantly distorted from the idealized cubic, perovskitestructure depending on the choice of metals at A and B sites and/or dueto the formation of oxygen vacancies upon reduction. In a preferredembodiment, the sum of a through n, in the sample compositions providedabove is 2 and X is 3. The A sites in a perovskite structure arecoordinated with 12 oxygen sites. The B sites in the structure wouldthen be occupied by the remaining, generally smaller atoms, and arecoordinated with 6 oxygen sites. Selection of A and B metal cations tooptimize their relative sizes is desirable for maximum structuralstability structure. Different metal cations can be substituted (ordoped) at a particular site, and for stability it is desirable that thesize of these cations be similar to the size of the cation beingreplaced. These criteria allow optimization of the selections withineach of the desirable combinations of metals from selected Groups of thePeriodic Table.

[0132] Stoichiometric perovskites (e.g., A³⁺B³⁺O²⁻ ₃) have all metal andoxygen sites occupied, whereas non-stoichiometric perovskites (e.g., A³⁺_(1−x)A′²⁺ _(x)B³⁺O²⁻ _(3−δ)□ can exist with oxygen vacancies. Oxygenvacancy concentration (δ) is governed by charge-neutrality. These oxygenvacancies in the crystal structure provide one mechanism for solid-statediffusion of O²⁻ ions in the crystal lattice. The O²⁻ ions can “jump” or“hop” from occupied sites to vacant sites, and hence diffuse within thelattice. This vacancy hopping mechanism for O²⁻ diffusion has beenestablished in various metal oxide compounds.

[0133] The metals are preferably selected to optimize use of oxygenand/or sulfur from the lattice structure as indicated by therelationship below where the presence of reducible metal cations allowoxygen or sulfur to be removed from the lattice:

O²⁻→½O₂+2e′+V_(o)

M^(n+)+2e′→M^((n−2)+)

[0134] where V_(o) denotes an oxygen vacancy formed due to oxygen beingremoved from the lattice, M is the reducible metal cation, and e is anelectron (for a p-type material, holes instead of electrons would beused to denote charge-transfer), where sulfur (S) can be substituted foroxygen (O) throughout. If the metals forming the perovskite or spinel donot reduce, oxygen or sulfur will not be removed from the crystallattice.

[0135] High oxygen diffusivity is necessary to allow O²⁻ ions to diffusefrom interior of metal oxide or sulfide particles to the surface wherethey can react with hydrogen. As stated above, oxygen diffusivity can beincreased by creating oxygen vacancies, for example by replacing some ofthe trivalent La with divalent Ca in the crystal structure of LaMnO₃. Inaddition to oxygen mobility, electronic conductivity is also essentialto allow electrons (or holes) to be transported away from (or to) theinterface.

[0136] For the purposes of this invention, the metal-based componentwill preferably have low reactivity towards hydrocarbons. Combinationsof metals may be selected to optimize the properties for a givenapplication. Lower molecular weight materials are generally preferredfor the economic benefit of greater oxygen capacity for a given mass ofmaterial to be used in the catalyst system.

[0137] Preferred crystal structures for the metal-based component woulddemonstrate an ability to sustain oxygen vacancies in crystal structure.Perovskites can accommodate a large vacancy concentration (δ) as largeas 0.5 or higher without phase decomposition. This phase stabilityallows for reversible oxygen and/or sulfur removal from and addition tothe metal-based component.

[0138] Another preferred crystal structure is the spinel (AB₂O₄)structure where A and B represent two distinct metal cation sites, where“B” is octahedrally coordinated to 6 oxygen sites and “A” istetrahedrally coordinated to 4 oxygen sites.

[0139] Another preferred structure is the birnessite (A_(z)BO_(x))crystal structure, which generally contains layered manganese oxide(MnO₆ ²⁻) octahedra sheets with “A” cations, typically Group 1 or Group2 metal ions, incorporated between MnO₆ layers to balance the negativecharge on the sheets. Differing amount of hydration water can also beincorporated between these layers. The birnessite structure can besynthesized along with the spinel structure, and has been observed totransform to a spinel structure. High-temperature stability ofbirnessite, and its transformation to spinel structure, appears todepend on selection of the stabilizing cation. For example, birnessitestructures containing potassium appear to be more stable than thosecontaining sodium.

[0140] It is anticipated that other crystalline structures could also beused to provide a metal-based component capable of surrendering oxygento a hydrogen combustion reaction.

[0141] The metal-based component could be prepared, by way ofnon-limiting example, by combining salts or chalcogenides (compounds ofthe Group 16 elements) containing the desired parts through such meansas evaporation or precipitation, optionally followed by calcination. Thesolid acid component is then physically mixed or chemically reacted withthe metal-based component and, optionally, combined with a binder toform catalyst particles.

[0142] The metal-based component can be obtained through chemical means,such as the combination of metal salts and/or chalcogenides, in solutionor slurry, followed by removal of the solvent or mother liquor viaevaporation or filtration and drying. Various methods for synthesizingparticular compounds are known in the art. The metal-based component canthen be ground and calcined. The solid acid and metal-based componentscan be physically admixed by mechanical mixing.

[0143] The solid acid component and the metal-based component of thecatalyst system in accordance with the present invention can bechemically bound. The chemically bound materials can then be subjectedto the treatment of a matrix component. The matrix component servesseveral purposes. It can bind the solid acid component and themetal-based component to form catalyst particles. It can serve as adiffusion medium for the transport of feed and product molecules. It canalso act as a filler to moderate the catalyst activity. In addition, thematrix can help heat transfer or serve as a sink or trap for metalcontaminants in the feedstock.

[0144] Examples of typical matrix materials include amorphous compoundssuch as silica, alumina, silica-alumina, silica-magnesia, titania,zirconia, and mixtures thereof. It is also preferred that separatealumina phases be incorporated into the inorganic oxide matrix. Speciesof aluminum oxyhydroxides-γ-alumina, boehmite, diaspore, andtransitional aluminas such as α-alumina, β-alumina, γ-alumina,δ-alumina, ε-alumina, κ-alumina, and ρ-alumina can be employed.Preferably, the alumina species is an aluminum trihydroxide such asgibbsite, bayerite, nordstrandite, or doyelite. The matrix material mayalso contain phosphorous or aluminum phosphate. The matrix material mayalso contain clays such as halloysite, kaolinite, bentonite,attapulgite, montmorillonite, clarit, fuller's earth, diatomaceousearth, and mixtures thereof. The weight ratio of the solid acidcomponent and the metal-based component to the inorganic oxide matrixcomponent can be about 100:1 to 1:100.

[0145] In another aspect of the present invention, the solid acidcomponent and the metal-based component of catalysts in accordance withthe present invention may be treated separately with a matrix component.The matrix component for the solid acid component can be the same as ordifferent from that for the metal-based component. One of the purposesof the treatment is to form particles of the solid acid component andparticles of the metal-based component so that the components are hardenough to survive interparticle and reactor wall collisions. The matrixcomponent may be made according to conventional methods from aninorganic oxide sol or gel, which is dried to “glue” the catalystparticle's components together. The matrix component can becatalytically inactive and comprises oxides of silicon, aluminum, andmixtures thereof. It is also preferred that separate alumina phases beincorporated into the inorganic oxide matrix. Species of aluminumoxyhydroxides-γ-alumina, boehmite, diaspore, and transitional aluminassuch as α-alumina, β-alumina, γ-alumina, δ-alumina, ε-alumina,κ-alumina, and ρ-alumina can be employed. Preferably, the aluminaspecies is an aluminum trihydroxide such as gibbsite, bayerite,nordstrandite, or doyelite. The matrix material may also containphosphorous or aluminum phosphate. The matrix material may also containclays such as kaolinite, bentonite, attapulgite, montmorillonite,clarit, fuller's earth, diatomaceous earth, and mixture thereof.

[0146] The weight ratio of the solid acid component to the matrixcomponent can be about 100:1 to 1:100. The weight ratio of themetal-based component to the matrix component can be about 100:1 to1:100.

[0147] The solid-acid component particles and the metal-based componentparticles may be mixed to form a uniform catalyst system in the reactoror be packed in series to form a staged catalyst system in either asingle reactor or two or more staged reactors.

[0148] The catalyst system of the present invention is multifunctionalin that it both cracks a hydrocarbon feedstream and selectively combuststhe hydrogen produced from the cracking reaction. The solid acidcomponent of the catalyst system performs the cracking function and themetal-based component of the catalyst system performs the selectivehydrogen combustion function. The catalyst system is particularlywell-suited for cracking hydrocarbons to light olefins and gasoline.Conventional catalytic cracking generates hydrogen amongst other crackedproducts, which makes products recovery more difficult and costly. Thecatalyst system of the present invention can perform hydrocarboncracking with reduced co-production of hydrogen thereby reducing theinvestment and operating costs and/or creating more equipment volume forhigher production capacity.

[0149] In accordance with the present invention, a catalyst systemcomprises a hydrocarbon cracking component and a selective hydrogencombustion component, which catalyst system, upon contact with ahydrocarbon feedstream, almost simultaneously cracks the hydrocarbon andselectively combusts the hydrogen produced from the cracking reaction.It is preferred that selective hydrogen combustion is conducted via ananaerobic mechanism which is related to the use of lattice oxygen fromthe selective hydrogen combustion component to promote selectivehydrogen combustion.

[0150] In accordance with the present invention, the hydrogen producedfrom the cracking reaction is selectively combusted or converted towater (or steam). There are several ways to utilize the benefits ofconverting the hydrogen product into condensable water.

[0151] It is believed that the inventive catalyst system is unique inthat, among other things, it permits simultaneous catalytic cracking ofhydrocarbon feedstreams to cracked products and combustion of resultanthydrogen to water. Preferably, the hydrogen combustion comprisesselective hydrogen combustion. The selective hydrogen combustion can beanaerobic without the feeding of free-oxygen containing gas to thereaction, or it can be conducted with the feeding of free-oxygencontaining gas.

[0152] Preferably, the yield of hydrogen is less than the yield ofhydrogen when contacting said hydrocarbon feedstream(s) with said solidacid component alone under said catalytic reaction conditions.Preferably, the yield of hydrogen is at least 10% less than the yield ofhydrogen when contacting said hydrocarbon feedstream(s) with said solidacid component alone under catalytic reaction conditions. Morepreferably, the yield of hydrogen is at least 25% less, more preferablyat 50% less, even more preferably at least 75%, yet more preferably atleast 90%, and most preferably greater than 99% less than the yield ofhydrogen when contacting said hydrocarbon feedstream(s) with said solidacid component alone under catalytic reaction conditions.

[0153] Typically the products from a cracking process are dischargedfrom the cracking reactor to pass through a quench tower and a mainfractionation column, producing one or more than one liquid streams anda vapor stream containing light gases such as hydrogen, methane,ethylene, ethane, propylene, propane, butylenes, and butanes. The vaporstream is compressed in one or more than one compressor and charged to aseries of fractionation columns for product recovery and purification.For example, current FCC technology typically produces vapor streamscontaining mixtures of hydrogen, light paraffins (e. g. methane, ethane,propane, and butanes) and light olefins (e. g. ethylene, propylene, andbutylenes), and liquid streams containing naphtha, gasoline, cycle oils,and heavier products. The product streams will go to a main fractionatorwhere gasoline and lighter streams are recovered in the overhead and theheavier streams go to the bottom. The overhead products are compressedand are often separated into C2− and C3+ products. Hydrogen usually isnot a desirable product due to the difficulty of separating it from theethylene and propylene. In addition, due to its low molecular weight,the presence of even a moderate quantity of H₂ in cracked products wouldconsume a significant fraction of the gas compressors' and thefractionators' volumetric capacities, which frequently become thebottlenecks for existing FCC units' processing of light hydrocarbons.Converting the hydrogen product into water, which can be condensed andseparated in the quench tower or the main fractionator, therefore,debottlenecks the compressors and/or the fractionators by freeing up thespace that would be occupied by the hydrogen. Such newly created spacein the compressors and/or the fractionators could be used to increasethe production of more desirable products such as light olefins.Increased production of light olefins could be accomplished by usinghigher concentrations of the ZSM-5 additive (or other olefin-selectiveadditives) in the FCC cracking catalysts.

[0154] Alternatively, at a constant production level, convertinghydrogen to water can reduce the number or the size of equipment,thereby reducing the investment costs.

[0155] Selective hydrogen combustion could also help supply the heatrequired for hydrocarbon cracking. The combustion of hydrogen is highlyexothermic and, therefore, would be an ideal internal source of heatsupply. This could reduce the need for external heat.

[0156] Thus, in accordance with the present invention, a catalyticcracking process comprises contacting a hydrocarbon feedstream with acatalyst system comprising a cracking/selective hydrogen combustioncatalyst under suitable catalytic cracking/selective hydrogen combustionconditions to produce olefins, gasoline, and other cracked products,wherein the catalytic cracking is conducted with a reduction of addedheat. Added heat can be reduced by at least 2%, preferably by over 5%,and even more preferably by over 10% by using the catalyst system of thepresent invention. Since cracking reactions are endothermic, therequired heat input is simply the overall enthalpy of the reaction.Thus, it is within the skill of one of ordinary skill in the art tocalculate the required heat input.

[0157] In accordance with the present invention, a free-oxygencontaining gas such as air or pure oxygen can be used as the source ofoxygen for the selective hydrogen combustion reaction. The free-oxygencontaining gas can be co-fed into the reaction vessel(s) with thehydrocarbon feedstream. Preferably, the lattice oxygen in themetal-based component of the catalyst system is used as the source ofoxygen for the selective hydrogen combustion reaction (anaerobichydrogen combustion). Higher hydrogen combustion selectivity and lessCO_(x) by-product are achievable using this approach as compared toco-feeding oxygen to the reactor. Using continuous catalyst regenerationtechnology would overcome the potential problem related to latticeoxygen being quickly consumed with resultant loss of catalyst activity.

[0158] The inventive process can be performed using any known reactor.By way of non-limiting, illustrative example, fixed-bed reactors withcatalyst regeneration, moving bed reactors with catalyst regenerationsuch as the continuous catalyst regeneration reactor (also known asCCR), fluidized-bed processes such as a riser reactor with catalystregeneration and the like would be suitable. A non-limiting illustrativeexample of a suitable fixed-bed catalyst regeneration system isillustrated in U.S. Pat. No. 5,059,738 to Beech, Jr. et al, which isincorporated herein by reference in its entirety. A non-limitingillustrative example of a suitable continuous catalyst regenerationmoving bed reactor is illustrated in U.S. Pat. No. 5,935,415 to Haizmannet al, which is incorporated herein by reference in its entirety. Apreferred reactor system would be a downer-regenerator or ariser-regenerator system as described below for illustration purposesonly. A riser-regenerator system that would be suitable for use inpracticing the inventive process is disclosed in U.S. Pat. No.5,002,653, which is incorporated herein by reference in its entirety.

[0159] In a riser-regenerator system, pre-heated hydrocarbon feed iscontacted with catalyst in a feed riser line wherein the reactionprimarily takes place. The temperature and pressure for theriser/reactor can be in the range of about 300 to about 800° C. and0.1-10 atmospheres (10-1000 kPa), respectively. The catalyst tohydrocarbon feed ratio, weight basis, can be in the range of 0.01 to1000. The residence time in the reaction zone can be in the range of0.01 second to 10 hours. As the reactions progress, the catalyst systemis progressively deactivated by consumption of lattice oxygen and theformation of coke on the catalyst surface. The catalyst system andhydrocarbon vapors are separated mechanically and hydrocarbons remainingon the catalyst are removed by steam stripping before the catalystsystem enters a catalyst regenerator. The hydrocarbon vapors are takenoverhead to a series of fractionation towers for product separation.Spent catalyst system is reactivated in the regenerator by burning offcoke deposits with air. The coke burn also serves as an oxidationtreatment to replenish the catalyst system's lattice oxygen consumed inthe reactor. The temperature and pressure for the regenerator can be inthe range of about 300 to about 800° C. and 0.1-10 atmospheres (10-1000kPa), respectively. As required, a small amount of fresh make-upcatalyst can be added to the reactor or, preferably, to the regenerator,where it can be preheated prior to entering the reactor.

[0160] The cracking process of the present invention may also beperformed in one or more conventional FCC process units underconventional FCC conditions in the presence of the catalyst system ofthis invention. Each unit comprises a riser reactor having a reactionzone, a stripping zone, a catalyst regeneration zone, and at least onefractionation zone. The feed is conducted to the riser reactor where itis injected into the reaction zone wherein the heavy feed contacts aflowing source of hot, regenerated catalyst. The hot catalyst vaporizesand cracks the feed and selectively combusts the resultant hydrogen at atemperature from about 475° C. to about 650° C., preferably from about500° C. to about 600° C. The cracking reaction deposits carbonaceoushydrocarbons, or coke, on the catalyst system and the selective hydrogencombustion reaction depletes the lattice oxygen, thereby deactivatingthe catalyst system. The cracked products may be separated from thedeactivated catalyst system and a portion of the cracked products may befed to a fractionator. The fractionator generally separates at least anaphtha fraction from the cracked products.

[0161] The deactivated catalyst system flows through the stripping zonewhere volatiles are stripped from the catalyst particles with astripping material such as steam. The stripping may be performed underlow severity conditions in order to retain absorbed hydrocarbons forheat balance through combustion in the regenerator. The strippedcatalyst is then conducted to the regeneration zone where it isregenerated by burning coke on the catalyst system and oxidizing theoxygen-depleted metal-based catalyst component in the presence of anoxygen containing gas, preferably air. Decoking and oxidation restorecatalyst activity and simultaneously heat the catalyst system to, e.g.,650° C. to 800° C. The hot catalyst is then recycled to the riserreactor at a point near or just upstream of the second reaction zone.Flue gas formed by burning coke in the regenerator may be treated forremoval of particulates and for conversion of carbon monoxide, afterwhich the flue gas is normally discharged into the atmosphere.

[0162] It has been observed that the flue gas resulting fromregeneration of the catalyst system described herein contains lessNO_(x) than the flue gas resulting from regeneration of a crackingcatalyst alone. Multiple mechanisms are believed to contribute to thisenvironmentally beneficial effect. The reduced metal-based component isbelieved to react with NO_(x) resulting in removal of oxygen from theNO_(x) while the lattice oxygen in the metal-based component isreplenished. Additionally, the metal-based components appear to adsorbsome portion of NO_(x), carrying it into the reactor where it reactswith hydrogen to form water and ammonia, both of which are easilyremoved from the products in the quench step.

[0163] Without being limited to any single theory, the materialsdisclosed herein are believed to activate NO_(x) by adsorption, allowingfor NO_(x) conversion to N₂. The presence of surface oxygen vacanciesand redox sites on the preferred crystal structures, and basicity ofthese metal oxide and sulfide compounds are likely reasons for highNO_(x) activation.

[0164] Use of the metal-based component in conjunction with regenerationof coked catalyst would be expected to result in a reduction of NO_(x)emissions in the flue gas. Preferably, the reduction would be at least10 percent, more preferably greater than 25 percent, even morepreferably greater than 50 percent, yet more preferably greater than 75percent, and most preferably greater than 90 percent.

[0165] The feed may be cracked in the reaction zone under conventionalFCC conditions in the presence of the catalyst system of this invention.Preferred process conditions in the reaction zone include temperaturesfrom about 475° C. to about 650° C., preferably from about 500° C. to600° C.; hydrocarbon partial pressures from about 0.5 to about 3.0atmospheres (50-300 kPa), preferably from about 1.0 to about 2.5atmospheres (100-250 kPa); and a catalyst to feed (wt/wt) ratio fromabout 1 to about 30, preferably from about 3 to about 15; where catalystweight is total weight of the catalyst composite. Though not required,it is also preferred that steam be concurrently introduced with the feedinto the reaction zone, with the steam comprising up to about 15 wt. %,and preferably ranging from about 1 wt. % to about 5 wt. % of the feed.Also, it is preferred that the feed's residence time in the reactionzone be less than about 100 seconds, for example from about 0.01 toabout 60 seconds, preferably from about 0.1 to about 30 seconds.

[0166] In accordance with the present invention, the weight ratio ofsolid acid component to the total weight of metal-based component isfrom 1000:1 to 1:1000. More preferably, the ratio is from 500:1 to1:500. Most preferably, the ratio is from 100:1 to 1:100. This ratio canbe adjusted and optimized for a given feedstock and desired productslate by adjusting the make-up rates of the individual components in thecatalyst system.

EXAMPLES

[0167] The invention is illustrated in the following non-limitingexamples, which are provided for the purpose of representation, and arenot to be construed as limiting the scope of the invention. All partsand percentages in the examples are by weight unless indicatedotherwise.

[0168] Further, with respect to the chemical formulas for themetal-based components presented in the examples, the numberingrepresents the molar relationships of the elements in the synthesismixture rather than the molar ratios of the elements in the resultingmetal oxide/sulfide. It is anticipated that multiple crystallinestructures could actually coexist within the resulting metal-basedcomponent. For example the metal-based component represented asLaMn_(0.4)Ni_(0.4)Al_(0.2)O_(x) was prepared from a mixture of solutionscontaining lanthanum in a ratio of 1:0.4 with manganese, a ratio of1:0.4 with nickel, and a ratio of 1:0.2 with aluminum. The subscript xon the oxygen component is indicative of the oxygen being sufficient tobalance the valences of the resulting compound, including the resultingvacancies and/or oxygen excess.

Example 1 (Comparative)

[0169] This example illustrates the hydrogen yield during hydrocarboncracking using a conventional zeolitic catalyst, without the addition ofselective hydrogen combustion (SHC) catalyst. 4.0 grams of OlefinsMax(Grace Davison Division of W. R. Grace & Co.) were pelletized, crushed,and screened to 30-50 mesh particles. It was then steamed at 700° C. for2 hours. 1.0 gram of steamed OlefinsMax was then physically mixed with2.5 grams of 16-25 mesh silicon carbide (SiC), an inert solid used tofill the volume of the test reactor, and loaded into a fixed-bed reactorfor testing. The catalyst was heated to 540° C. in a helium stream at aflow rate of 105 cm³/min and a pressure of 2-4 psig (14-28 kPa). Thetemperature was allowed to stabilize for 30 minutes prior to theaddition of hydrocarbon feed. The feed consisted of 0.384 cm³/min of2-methylpentane and 0.025 cm³/min of liquid water. Following theintroduction of hydrocarbon feed, product samples were collected every30 seconds for a total time-period of 3.5 minutes using a multi-port,gas-sampling valve. The product was analyzed using a gas chromatographequipped with flame ionization and pulsed discharge detectors. Table 1shows the hydrogen and combined yield of C₁-C₄ products at variousconversions of 2-methylpentane. When LVN was used as feed, similarhydrogen and C₁-C₄ yields were obtained when compared at the same feedconversion. A small CO_(x) yield (typically, <0.1 wt %) was observed dueto background contamination and/or hydrocarbon oxidation duringpost-reaction sampling/analysis. The yield observed in the comparisonreaction was deducted from the yield observed in the test reactionsprior to reporting. TABLE 1 Hydrogen 2-Methylpentane Conversion C₁-C₄Yield (wt %) Yield (wt %) 39.2 33.3 0.230 ± 0.012 21.1 18.6 0.131 ±0.007 8.1 6.7 0.044 ± 0.002

Examples Comprising Metals from Sub-Group 1 Example 2

[0170] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. La_(a)Mn_(b)Ni_(c)Al_(d)O_(x) catalyst was prepared byco-precipitation of metal salts using an organic base and a carbonateprecursor. Solution A was prepared by dissolving 9.106 grams oflanthanum nitrate hexahydrate (Aldrich Chemical Company, Milwaukee,Wis.), 1.059 grams of manganese (II) chloride (Aldrich Chemical Company,Milwaukee, Wis.), 2.446 grams of nickel nitrate hexahydrate (AldrichChemical Company, Milwaukee, Wis.), and 1.578 grams of aluminum nitratenonahydrate (Aldrich Chemical Company, Milwaukee, Wis.) in 210 grams ofdeionized water. Solution B was prepared by dissolving 13.3 grams ofsodium bicarbonate (Mallinckrodt Baker Inc., Paris, Ky.) and 39.8 gramsof tetraethylammonium hydroxide, 35 wt % solution (Alfa Aesar, WardHill, Mass.) in 631 grams of deionized water. Solution A was slowedpoured into a well-stirred solution B, resulting in precipitateformation. After aging the suspension for 1 hour, the particles wererecovered by centrifugation at 1500-2000 rpm. The precipitate was thenresuspended in 250 mL of isopropanol (VWR Scientific ProductsCorporation, Chicago, Ill.) followed by centrifugation to remove wateralong with impurity cations/anions. This washing step was repeated. Theprecipitate was dried in air at 25° C., ground to a fine powder using amortar and pestle, and calcined to 800° C. for 2 hours in air. Thesample was pelletized, crushed, and screened to 30-50 mesh prior to SHCtesting.

[0171] 1.0 grams of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 grams of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 2 shows the resultsof the SHC test.

[0172] The data in Table 2 demonstrates that significant reductions inhydrogen yield can be achieved through the addition of SHC catalyst.Compared to Example 1, there is a 53 percent reduction in hydrogen yieldat similar hydrocarbon conversion and C₁-C₄ yields. Moreover, the SHCcatalyst exhibits a high selectivity of 81 percent for hydrogencombustion, resulting in minimal CO_(x) formation through non-selectivehydrocarbon activation.

Example 3

[0173] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. Sc_(a)Cu_(b)Mn_(c)O_(x) catalyst was prepared byco-precipitation of metal salts using an organic base in an alcoholmedium. Solution A was prepared by dissolving 3.642 grams of scandiumnitrate hydrate (Alfa Aesar, Ward Hill, Mass.), 0.323 grams of copper(II) nitrate hydrate (Alfa Aesar, Ward Hill, Mass.), 1.681 grams ofmanganese (II) chloride (Aldrich Chemical Company, Milwaukee, Wis.) in67 grams of deionized water. Solution B was prepared by dissolving 58grams of tetraethylammonium hydroxide, 35 wt % solution (Alfa Aesar,Ward Hill, Mass.) in 225 grams of isopropanol (VWR Scientific ProductsCorporation, Chicago, Ill.). Solution A was slowly poured into awell-stirred solution B, resulting in precipitate formation. After agingthe suspension for 1 hour, the particles were recovered bycentrifugation at 1500-2000 rpm. The precipitate was then resuspended in250 mL of isopropanol followed by centrifugation to remove water alongwith impurity cations/anions. This washing step was repeated. Theprecipitate was dried in air at 25° C., ground to a fine powder using amortar and pestle, and calcined to 800° C. for 2 hours in air. Thesample was pelletized, crushed, and screened to 30-50 mesh prior to SHCtesting.

[0174] 1.0 grams of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 grams of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 2 shows the resultsof the SHC test. TABLE 2 SHC Catalyst LaMn_(0.4)Ni_(0.4)Al_(0.2)O₃Sc_(0.9)Cu_(0.1)MnO₃ % Conversion 7.7 8.0 C₁-C₄ Yield (wt %) 6.7 6.7 H₂Yield (wt %) 0.021 0.023 % H₂ Conversion 53 48 CO_(x) Yield (wt %) 0.0550.174 % H₂ Selectivity 81 67

[0175] The data in Table 2 demonstrates that significant reductions inhydrogen yield can be achieved through the addition of SHC catalyst.Compared to Example 1, there is a 48 percent reduction in hydrogen yieldat similar hydrocarbon conversion and C₁-C₄ yields. Moreover, the SHCcatalyst exhibits a selectivity of 67 percent for hydrogen combustion,resulting in minimal CO_(x) formation through non-selective hydrocarbonactivation.

Example 4

[0176] Table 3 shows the performance of additional combinations ofsub-group 1 SHC catalysts with the cracking catalyst of Example 1. Alltests were run at the conditions described in Example 1 with 0.5 gramsof the SHC catalyst being tested mixed with 2.0 grams of SiC and either1.0 grams of steamed OlefinsMax or 0.5 grams of fresh OlefinsMax. TABLE3 Catalyst Composition % H₂ Conversion % H₂ SelectivityY_(0.2)In_(0.6)Zn_(0.2)MnO₃ 84.2 100 LaMn_(0.4)Ni_(0.4)Al_(0.2)O₃ 69.191 La_(0.9)Mn_(0.8)Al_(0.2)O₃ 41.4 100 Sc_(0.9)Cu_(0.1)MnO₃ 53.8 55Sc_(0.8)Zn_(0.2)MnO₃ 55.6 34 Zr_(0.6)La_(0.4)O₂ 10.7 100La_(0.05)—Zr_(0.95)O₂ 11.6 90 Mn_(0.9)Sc_(0.1)O₂ 15.0 27Pr_(0.7)In_(0.2)Zn_(0.1)O₂ 14.3 20

Examples Comprising Metals from Sub-Group 2 Example 5

[0177] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. In_(0.8)Ca_(0.2)MnO₃ catalyst was prepared byco-precipitation of metal salts using an organic base and a carbonateprecursor. Solution A was prepared by dissolving 6.289 grams of indiumnitrate hydrate (Alfa Aesar, Ward Hill, Mass.), 1.164 grams of calciumnitrate tetrahydrate (Alfa Aesar, Ward Hill, Mass.), and 7.018 grams ofmanganese (II) nitrate hydrate (Aldrich Chemical Company, Milwaukee,Wis.) in 247 grams of deionized water. Solution B was prepared bydissolving 15.0 grams of sodium bicarbonate (Mallinckrodt Baker Inc.,Paris, Ky.), 45.1 grams of tetraethylammonium hydroxide, 35 wt %solution (Alfa Aesar, Ward Hill, Mass.) in 715 grams of deionized water.Solution A was slowed poured into a well-stirred solution B, resultingin precipitate formation. After aging the suspension for 1 hour, theparticles were recovered by centrifugation at 1500-2000 rpm. Theprecipitate was then resuspended in 250 mL of isopropanol (VWRScientific Products Corporation, Chicago, Ill.) followed bycentrifugation to remove water, impurity cations/anions. This washingstep was repeated. The precipitate was dried in air at 25° C., ground toa fine powder using a mortar and pestle, and calcined to 800° C. for 2hours in air. The sample was pelletized, crushed, and screened to 30-50mesh prior to SHC testing.

[0178] 1.0 grams of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 grams of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 4 shows the resultsof the SHC test.

[0179] The data in Table 4 demonstrates that significant reductions inhydrogen yield can be achieved through the addition of SHC catalyst.Compared to Example 1, there is a 92 percent reduction in hydrogen yieldat similar hydrocarbon conversion and C1-C4 yields. Moreover, the SHCcatalyst exhibits a high selectivity of 85 percent for hydrogencombustion, resulting in minimal CO_(x) formation through non-selectivehydrocarbon activation.

Example 6

[0180] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. Bi_(0.4)Ca_(0.6)Mn_(0.6)Ni_(0.4)O₃ catalyst was prepared byco-precipitation of metal salts using an organic base in an alcoholmedium. Solution A was prepared by adding 5 mL of concentrated nitricacid to 50 mL of deionized water. 4.574 grams of bismuth nitratepentahydrate (Aldrich Chemical Company, Milwaukee, Wis.) were added tothis solution and stirred for 10 minutes to allow complete dissolution.3.341 grams of calcium nitrate tetrahydrate (Alfa Aesar, Ward Hill,Mass.), 4.027 grams of manganese (II) nitrate hydrate (Aldrich ChemicalCompany, Milwaukee, Wis.), 2.742 of nickel (II) nitrate hexahydrate(Aldrich Chemical Company, Milwaukee, Wis.) and 107 grams of deionizedwater were then added and dissolved in solution A. Solution B wasprepared by dissolving 98 grams of tetraethylammonium hydroxide, 35 wt %solution (Alfa Aesar, Ward Hill, Mass.) in 534 grams of isopropanol (VWRScientific Products Corporation, Chicago, Ill.). Solution A was slowedpoured into a well-stirred solution B, resulting in precipitateformation. After aging the suspension for 1 hour, the particles wererecovered by centrifugation at 1500-2000 rpm. The precipitate was thenresuspended in 250 mL of isopropanol followed by centrifugation toremove water, impurity cations/anions. The precipitate was dried in airat 25° C., ground to a fine powder using a mortar and pestle, andcalcined to 750° C. for 2 hours in air. The sample was pelletized,crushed, and screened to 30-50 mesh prior to SHC testing.

[0181] 1.0 grams of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 grams of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 4 shows the resultsof the SHC test.

[0182] The data in Table 4 demonstrate that significant reductions inhydrogen yield can be achieved through the addition of SHC catalyst.Compared to Example 1, there is an 83 percent reduction in hydrogenyield at similar hydrocarbon conversion and C1-C4 yields. Moreover, theSHC catalyst exhibits a high selectivity of 80 percent for hydrogencombustion, resulting in minimal CO_(x) formation through non-selectivehydrocarbon activation.

Example 7

[0183] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. Ca_(0.6)Na_(0.4)SnO₃ catalyst was prepared byco-precipitation of metal salts using an organic base in an alcoholmedium. Solution A was prepared by adding 5 mL of concentrated nitricacid to 50 mL of deionized water. 13.151 grams of tin chloridepentahydrate (Alfa Aesar, Ward Hill, Mass.) were added to this solutionand stirred for 10 minutes to allow complete dissolution. 5.315 grams ofcalcium nitrate tetrahydrate (Alfa Aesar, Ward Hill, Mass.) and 260grams of deionized water were then added and dissolved in solution A.Solution B was prepared by dissolving 164 grams of tetraethylammoniumhydroxide, 35 wt % solution (Alfa Aesar, Ward Hill, Mass.) in 637 gramsof isopropanol (VWR Scientific Products Corporation, Chicago, Ill.).Solution A was slowed poured into a well-stirred solution B, resultingin precipitate formation. After aging the suspension for 1 hour, theparticles were recovered by centrifugation at 1500-2000 rpm. Theprecipitate was then resuspended in 250 mL of isopropanol followed bycentrifugation to remove water, impurity cations/anions. A 0.07295 gNa/g solution was prepared by dissolving NaOH (Mallinckrodt Baker Inc.,Paris, Ky.) in deionized water. 7.40 grams of NaOH solution and 100 mLof ethanol (Alfa Aesar, Ward Hill, Mass.) were added to the precipitate,and stirred to obtain a homogenous suspension. The suspension was heatedto 90° C. to evaporate the ethanol, ground using a mortar and pestle toobtain a fine powder, and calcined to 800° C. for 2 hours in air. Thesample was pelletized, crushed, and screened to 30-50 mesh prior to SHCtesting.

[0184] 1.0 grams of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 grams of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 4 shows the resultsof the SHC test. TABLE 4 SHC Catalyst In_(0.8)Ca_(0.2)MnO₃Bi_(0.4)Ca_(0.6)Mn_(0.6)Ni_(0.4)O₃ Ca_(0.6)Na_(0.4)SnO₃ % Conversion20.9 8.1 7.9 C₁-C₄ 16.2 6.7 6.7 Yield (wt %) H₂ 0.011 0.0076 0.034 Yield(wt %) % H₂ 92 83 22 Conversion CO_(x) 0.220 0.129 0 Yield (wt %) % H₂85 80 100 Selectivity

Example 8

[0185] Table 5 shows the performance of additional combinations ofsub-group 2 SHC catalysts with the cracking catalyst of Example 1. Alltests were run at the conditions described in Example 1 with 0.5 gramsof the SHC catalyst being tested mixed with 2.0 grams of SiC and either1.0 grams of steamed OlefinsMax or 0.5 grams of fresh OlefinsMax. TABLE5 % H₂ Catalyst Composition Conversion % H₂ SelectivityLa_(0.2)Ca_(0.8)Mn_(0.54)Co_(0.36)Ti_(0.1)O₃ 91.7 ˜100La_(0.2)Ca_(0.8)Mn_(0.54)Co_(0.36)Sn_(0.1)O₃ 90.8 ˜100La_(0.2)Ca_(0.8)Mn_(0.4)Co_(0.4)Ti_(0.2)O₃ 90.4 ˜100La_(0.6)Ca_(0.4)CoO₃ 89.6 97 La_(0.2)Ca_(0.8)Mn_(0.6)Co_(0.4)O₃ 89.0 97La_(0.2)Ca_(0.8)Mn_(0.8)Ni_(0.2)O₃ 85.1 97La_(0.2)Ca_(0.8)Mn_(0.4)Co_(0.4)Sn_(0.2)O₃ 83.1 ˜100La_(0.2)Ca_(0.8)Mn_(0.4)Co_(0.4)Al_(0.2)O₃ 82.3 99La_(0.2)Ca_(0.8)Mn_(0.4)Co_(0.4)Al_(0.2)O₃ 76.0 100La_(0.2)Ca_(0.8)Mn_(0.4)Co_(0.4)Al_(0.2)O₃ 72.0 97La_(0.2)Ca_(0.8)Mn_(0.54)Co_(0.36)Al_(0.1)O₃ 81.4 ˜100La_(0.2)Ca_(0.8)Mn_(0.8)Co_(0.2)O₃ 81.2 100Ba_(0.8)K_(0.2)Bi_(0.8)La_(0.2)O₃ 79.3 98La_(0.2)Ca_(0.8)Mn_(0.4)Ti_(0.4)Al_(0.2)O₃ 77.4 ˜100La_(0.6)Ca_(0.4)Co_(0.6)Ni_(0.2)Al_(0.2)O₃ 77.1 ˜100La_(0.6)Ca_(0.4)Co_(0.8)Ti_(0.2)O₃ 76.8 99 BaBi_(0.5)La_(0.5)O₃ 75.4 99La_(0.2)Ca_(0.8)Mn_(0.2)Co_(0.6)Al_(0.2)O₃ 72.7 ˜100La_(0.6)Ca_(0.4)Co_(0.8)Al_(0.2)O₃ 72.2 100La_(0.6)Ca_(0.4)Co_(0.9)Al_(0.1)O₃ 71.6 100 La_(0.6)Ca_(0.4)MnO₃ 68.8 95La_(0.2)Ca_(0.8)MnO₃ 66.9 96 La_(0.4)Ca_(0.6)Mn_(0.4)Co_(0.4)Al_(0.2)O₃66.4 N/A La_(0.2)Ca_(0.8)Mn_(0.6)Co_(0.2)Al_(0.2)O₃ 65.2 97La_(0.6)Ca_(0.4)Co_(0.6)Mn_(0.4)O₃ 64.9 85La_(0.6)Ca_(0.4)Co_(0.6)Al_(0.4)O₃ 63.8 100 BaBi_(0.6)La_(0.4)O₃ 62.3 99La_(0.2)Ca_(0.8)Mn_(0.8)Mg_(0.2)O₃ 60.0 86La_(0.6)Ca_(0.4)Mn_(0.5)Fe_(0.5)O₃ 58.5 ˜100La_(0.6)Sr_(0.4)Co_(0.8)Al_(0.2)O₃ 57.8 100 BaBi_(0.6)Yb_(0.4)O₃ 56.7 90BaBi_(0.67)Sn_(0.16)La_(0.2)O₃ 55.9 99La_(0.8)Ca_(0.2)Mn_(0.8)Ga_(0.2)O₃ 55.5 100La_(0.8)Ca_(0.2)Mn_(0.8)Al_(0.2)O₃ 55.4 98La_(0.2)Ca_(0.8)Mn_(0.4)Sn_(0.4)Al_(0.2)O₃ 53.8 ˜100La_(0.6)Ca_(0.4)Mn_(0.8)Ni_(0.2)O₃ 51.0 64La_(0.6)Ca_(0.4)Mn_(0.8)Co_(0.2)O₃ 50.8 62La_(0.6)Ca_(0.4)Mn_(0.8)Cu_(0.2)O₃ 50.7 88La_(0.2)Ca_(0.8)Mn_(0.54)Co_(0.36)Ga_(0.1)O₃ 49.8 86La_(0.6)Ca_(0.4)Mn_(0.8)Al_(0.2)O₃ 49.3 100La_(0.4)Ca_(0.6)Co_(0.8)Al_(0.2)O₃ 48.4 100 BaBi_(0.4)Sn_(0.4)La_(0.2)O₃48.2 100 La_(0.8)Ca_(0.2)Co_(0.8)Al_(0.2)O₃ 48.1 100La_(0.6)Ca_(0.4)Fe_(0.2)Co_(0.8)O₃ 46.5 93 BaBi_(0.8)La_(0.2)O₃ 45.0 94La_(0.2)Ca_(0.8)Mn_(0.5)Co_(0.2)Ni_(0.2)Al_(0.1)O₃ 29.5 36Y_(0.6)Ca_(0.4)MnO₃ 21.6 29 La_(0.6)Ca_(0.4)Fe_(0.8)Co_(0.2)O₃ 20.6 60Sr_(0.8)Na_(0.2)Sn_(0.8)Y_(0.2)O₃ 19.6 100

Examples Comprising Metals from Sub-Group 3 Example 9

[0186] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. Ba_(0.8)K_(0.2)Bi_(0.8)La_(0.2)O₃ catalyst was prepared byco-precipitation of metal salts using an organic base in an alcoholmedium. Solution A was prepared by adding 12 mL of concentrated nitricacid to 50 mL of deionized water. 8.069 grams of bismuth nitratepentahydrate (Aldrich Chemical Company, Milwaukee, Wis.) were added tothis solution and stirred for 10 minutes to allow complete dissolution.4.348 grams of barium nitrate (Alfa Aesar, Ward Hill, Mass.), 1.801grams of lanthanum nitrate hexahydrate (Aldrich Chemical Company,Milwaukee, Wis.) and 200 grams of water were then added and dissolved insolution A. Solution B was prepared by dissolving 101 grams oftetraethylammonium hydroxide, 35 wt % solution (Alfa Aesar, Ward Hill,Mass.) in 750 grams of isopropanol (VWR Scientific Products Corporation,Chicago, Ill.). Solution A was slowly poured into a well-stirredsolution B, resulting in precipitate formation. After aging thesuspension for 1 hour, the particles were recovered by centrifugation at1500-2000 rpm. The precipitate was then resuspended in 250 mL ofisopropanol followed by centrifugation to remove water and impuritycations/anions. This washing step was repeated. 0.06248 g of potassiumper gram of solution was prepared by dissolving KOH (Mallinckrodt BakerInc., Paris, Ky.) in deionized water. 3.729 grams of KOH solution and100 mL of isopropanol were added to the precipitate, and stirred toobtain a homogenous suspension. The suspension was heated to 90° C. toevaporate the isopropanol, ground using a mortar and pestle to obtain afine powder, and calcined to 800° C. for 2 hours in air. The sample waspelletized, crushed, and screened to 30-50 mesh prior to SHC testing.

[0187] 1.0 gram of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 gram of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 6 shows the resultsof the SHC test.

[0188] The data in Table 6 demonstrates that significant reductions inhydrogen yield can be achieved through the addition of the SHC catalyst.Compared to Example 1, there is a 79 percent reduction in hydrogen yieldat similar hydrocarbon conversion and C₁-C₄ yields. Moreover, the SHCcatalyst exhibits a very high selectivity of 99 percent for hydrogencombustion, resulting in essentially no CO_(x) formation throughnon-selective hydrocarbon activation.

Example 10

[0189] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. La_(0.6)Ca_(0.4)MnO₃ catalyst was prepared byco-precipitation of metal salts using an organic base in an alcoholmedium. Solution A was prepared by dissolving 9.631 grams of lanthanumnitrate hexahydrate (Aldrich Chemical Company, Milwaukee, Wis.), 3.502grams of calcium nitrate tetrahydrate (Alfa Aesar, Ward Hill, Mass.),and 10.552 grams of manganese (II) nitrate hydrate (Aldrich ChemicalCompany, Milwaukee, Wis.) in 185 grams of deionized water. Solution Bwas prepared by dissolving 108 grams of tetraethylammonium hydroxide, 35wt % solution (Alfa Aesar, Ward Hill, Mass.) in 418 grams of isopropanol(VWR Scientific Products Corporation, Chicago, Ill.). Solution A wasslowly poured into a well-stirred solution B, resulting in precipitateformation. After aging the suspension for 1 hour, the particles wererecovered by centrifugation at 1500-2000 rpm. The precipitate was thenresuspended in 250 mL of isopropanol followed by centrifugation toremove water and impurity cations/anions. This washing step wasrepeated. The precipitate was dried in air at 25° C., ground to a finepowder using a mortar and pestle, and calcined to 750° C. for 2 hours inair. The sample was pelletized, crushed, and screened to 30-50 meshprior to SHC testing.

[0190] 1.0 gram of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 gram of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 6 shows the resultsof the SHC test.

[0191] The data in Table 6 demonstrate that significant reductions inhydrogen yield can be achieved through the addition of SHC catalyst.Compared to Example 1, there is a 72 percent reduction in hydrogen yieldat similar hydrocarbon conversion and C₁-C₄ yields. Moreover, the SHCcatalyst exhibits a very high selectivity of 94 percent for hydrogencombustion, resulting in essentially no CO_(x) formation throughnon-selective hydrocarbon activation.

Example 11

[0192] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. La_(0.6)Ca_(0.4)Fe_(0.2)Co_(0.8)O₃ catalyst was prepared byco-precipitation of metal salts using an organic base in an alcoholmedium. Solution A was prepared by dissolving 9.473 grams of lanthanumnitrate hexahydrate (Aldrich Chemical Company, Milwaukee, Wis.), 3.444grams of calcium nitrate tetrahydrate (Alfa Aesar, Ward Hill, Mass.),2.946 grams of iron (III) nitrate nonahydrate (Aldrich Chemical Company,Milwaukee, Wis.), and 8.490 grams of cobalt nitrate hexahydrate (AlfaAesar, Ward Hill, Mass.) in 182 grams of deionized water. Solution B wasprepared by dissolving 110 grams of tetraethylammonium hydroxide, 35 wt% solution (Alfa Aesar, Ward Hill, Mass.) in 429 grams of isopropanol(VWR Scientific Products Corporation, Chicago, Ill.). Solution A wasslowed poured into a well-stirred solution B, resulting in precipitateformation. After aging the suspension for 1 hour, the particles wererecovered by centrifugation at 1500-2000 rpm. The precipitate was thenresuspended in 250 mL of isopropanol followed by centrifugation toremove water and impurity cations/anions. This washing step wasrepeated. The precipitate was dried in air at 25° C., ground to a finepowder using a mortar and pestle, and calcined to 750° C. for 2 hours inair. The sample was pelletized, crushed, and screened to 30-50 meshprior to SHC testing.

[0193] 1.0 gram of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 gram of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 6 shows the resultsof the SHC test. TABLE 6 SHC Catalyst Ba_(0.8)K_(0.2)Bi_(0.8)La_(0.2)O₃La_(0.6)Ca_(0.4)MnO₃ La_(0.6)Ca_(0.4)Fe_(0.2)Co_(0.8)O₃ % Conversion39.2 22.1 19.8 C₁-C₄ Yield (wt %) 33.3 18.6 17.3 H₂ Yield (wt %) 0.0490.037 0.048 % H₂ Conversion 79 72 63 CO_(x) Yield (wt %) 0.028 0.0700.016 % H₂ Selectivity 99 94 98

[0194] The data in Table 6 demonstrate that significant reductions inhydrogen yield can be achieved through the addition of the SHC catalyst.Compared to Example 1, there is a 63 percent reduction in hydrogen yieldat similar hydrocarbon conversion and C₁-C₄ yields. Moreover, the SHCcatalyst exhibits a very high selectivity of 98 percent for hydrogencombustion, resulting in essentially no CO_(x) formation throughnon-selective hydrocarbon activation.

Example 12

[0195] Table 7 shows the performance of additional combinations ofsub-group 3 SHC catalysts with the cracking catalyst of Example 1. Alltests were run at the conditions described in Example 1 with 0.5 gramsof the SHC catalyst being tested mixed with 2.0 grams of SiC and either1.0 grams of steamed OlefinsMax or 0.5 grams of fresh OlefinsMax. TABLE7 % H₂ % H₂ Catalyst Composition Conversion Selectivity Ba_(0.25)MnO_(x)(K₂CO₃ syn, High pH) 93.1 ˜100 Mg_(0.125)MnO_(x) (K₂CO₃ syn.) 91.7 ˜100Mg_(0.25)MnO_(x) (K₂CO₃ syn.) 700 C, repeat 91.7 ˜100 Mg_(0.25)MnO_(x)(K₂CO₃ syn.) 700 C, steamed 18 h 91.3 99 Mg_(0.25)MnO_(x) (NaHCO₃)-800C-BCSU-2 91.3 95 Ba_(0.125)MnO_(x) (K₂CO₃ syn., High pH) 90.8 99Ba_(0.25)MnO_(x) (K₂CO₃ syn, High pH) steamed 90.6 ˜100 18 hBa_(0.25)MnO_(x) (K₂CO₃ syn) 89.3 ˜100 Ba_(0.125)MnO_(x) (0.75 × K₂CO₃syn.) 89.1 ˜100 Mn_(0.7)Mg_(0.3)O_(x) 89.1 97 Sr_(0.25)MnO_(x) (K₂CO₃)89.1 ˜100 In_(0.8)Ca_(0.2)MnO₃ 88.9 87 Ba_(0.25)K_(0.2)MnO_(x)(hydroxide syn.) 87.5 97 Mg_(0.25)MnO_(x) (K₂CO₃ syn.) 700 C 86.6 92Bi_(0.2)Ca_(0.8)Mn_(0.8)Co_(0.2)O₃ 85.9 N/A Mn_(0.6)Mg_(0.4)O_(x) 85.719 Mg_(0.25)MnO_(x) (K₂CO₃ syn.) (High pH) 85.6 ˜100Bi_(0.2)Ca_(0.8)Mn_(0.8)Ni_(0.2)O₃ 85.4 81Bi_(0.4)Ca_(0.6)Mn_(0.6)Ni_(0.4)O₃ 84.6 72 Ba_(0.125)MnO_(x) (K₂CO₃syn.) 80.6 ˜100 Mg_(0.25)MnO_(x) (K-syn) 80.5 89 Mg_(0.25)MnO_(x) (1.25× K₂CO₃ syn.) 80.0 48 Mg_(0.25)MnO_(x) (0.75 × K₂CO₃ syn.) 79.6 29Mg_(0.25)MnO_(x) (NaHCO₃)-BCSU-2 78.6 89 CaMn_(0.4)Sn_(0.4)Co_(0.2)O₃77.6 86 In_(0.8)Mg_(0.2)Mn_(0.6)Al_(0.4)O₃ 77.5 86In_(0.8)Zn_(0.2)Mn_(0.6)Al_(0.4)O₃ 77.5 86 Ba_(0.25)MnO_(x) (Na₂CO₃ syn)77.3 ˜100 Ba_(0.25)MnO_(x) (NaHCO₃ syn.) 76.3 94 Mg_(0.5)MnO_(x) (Na₂CO₃syn) 75.6 90 CoMn₂O₄ (15% Na) 71.6 86 Mg_(0.25)MnO_(x) (K₂CO₃ syn.) 800C 71.4 93 Mg_(0.5)MnO_(x) (K₂CO₃ syn) 71.1 ˜100 Mg_(0.25)MnO_(x) (Na₂CO₃syn.) 70.6 90 CaMn_(0.8)Sb_(0.2)O₃ 69.5 ˜100CaMn_(0.4)Co_(0.4)Al_(0.2)O₃ 69.4 ˜100 Ba_(0.25)MnO_(x) (K₂CO₃ syn, HighpH) steamed 67.8 97 72 h SrSb_(0.4)Sn_(0.3)Mg_(0.3)O_(x) 67.3 83 CoMn₂O₄(15% K) 66.0 58 Mn_(0.9)Mg_(0.1)O₂ 65.3 45 Mg_(0.125)MnO_(x) (Na₂CO₃)60.1 95 Ba_(0.25)K_(0.1)MnO_(x) (hydroxide syn.) 58.9 98Ni_(0.8)Mg_(0.2)MnO₃ 56.9 21 Mn_(0.7)Mg_(0.2)Al_(0.1)O_(x) 56.4 96Mn_(0.7)Mg_(0.2)Ti_(0.1)O_(x) 52.5 95 SrSb_(0.5)Ca_(0.5)O_(x) 52.5 ˜100SrTi_(0.4)Sn_(0.4)Al_(0.2)O₃ 52.1 ˜100 SrMn_(0.4)Ti_(0.4)Al_(0.2)O₃ 50.4˜100 Ca₂Mn₃O₈ 50.3 70 Mg_(0.25)MnO_(x) (Na₂CO₃) (High pH) 47.6 59Ca_(0.25)MnO_(x) (hydroxide syn.) 47.4 42 CaZr_(0.8)Al_(0.2)O₃ 46.9 ˜100Bi_(0.4)Ca_(0.6)MnO₃ 46.6 30 Bi_(0.4)Sr_(0.6)Co_(0.2)Fe_(0.8)O₃ 46.4 57Ba_(0.5)MnO_(x) (hydroxide syn.) 41.5 99 CaMn_(0.8)Al_(0.2)O₃ 34.9 50Ca_(0.8)Na_(0.2)SnO₃ 23.0 N/A Ca_(0.6)Na_(0.4)SnO₃ 21.7 N/A BaZrO₃ 17.5N/A

Examples Comprising Metals from Sub-Group 4 Example 13

[0196] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. In_(0.9)Zn_(0.1)MnO₃ catalyst was prepared byco-precipitation of metal salts using an organic base and a carbonateprecursor. Solution A was prepared by dissolving 6.742 grams of indium(III) nitrate hydrate (Alfa Aesar, Ward Hill, Mass.), 0.516 grams ofzinc acetate dihydrate (Aldrich Chemical Company, Milwaukee, Wis.) and6.688 grams of manganese (II) nitrate hydrate (Aldrich Chemical Company,Milwaukee, Wis.) in 117 grams of deionized water. Solution B wasprepared by dissolving 14.6 sodium bicarbonate (Mallinckrodt Baker Inc.,Paris, Ky.), 43.7 grams of tetraethylammonium hydroxide, 35 wt %solution (Alfa Aesar, Ward Hill, Mass.) in 693 grams of deionized water.Solution A was slowed poured into a well-stirred solution B, resultingin precipitate formation. After aging the suspension for 1 hour, theparticles were recovered by centrifugation at 1500-2000 rpm. Theprecipitate was then resuspended in 250 mL of ethanol (Alfa Aesar, WardHill, Mass.) followed by centrifugation to remove water, impuritycations/anions. The precipitate was dried in air at 25° C., ground to afine powder using a mortar and pestle, and calcined to 800° C. for 2hours in air. The sample was pelletized, crushed, and screened to 30-50mesh prior to SHC testing.

[0197] The 1.0 grams of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 grams of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 8 shows the resultsof the SHC test.

[0198] The data in Table 8 demonstrate that significant reductions inhydrogen yield can be achieved through the addition of SHC catalyst.Compared to Example 1, there is a 78 percent reduction in hydrogen yieldat similar hydrocarbon conversion and C1-C4 yields. Moreover, the SHCcatalyst exhibits a very high selectivity of 97 percent for hydrogencombustion, resulting in virtually no CO_(x) formation throughnon-selective hydrocarbon activation.

Example 14

[0199] This example illustrates the preparation and performance ofselective hydrogen combustion (SHC) catalyst for reducing the hydrogenyield in the product, while minimizing non-selective hydrocarbonoxidation. Ino_(0.95)Cu_(0.05)MnO₃ catalyst was prepared byco-precipitation of metal salts using an organic base and a carbonateprecursor. Solution A was prepared by dissolving 7.038 grams of indiumnitrate hydrate (Alfa Aesar, Ward Hill, Mass.), 0.281 grams of copper(II) nitrate hydrate (Alfa Aesar, Ward Hill, Mass.), and 6.614 grams ofmanganese (II) nitrate hydrate (Aldrich Chemical Company, Milwaukee,Wis.) in 116 grams of deionized water. Solution B was prepared bydissolving 14.5 grams of sodium bicarbonate (Mallinckrodt Baker Inc.,Paris, Ky.), 43.6 grams of tetraethylammonium hydroxide, 35 wt %solution (Alfa Aesar, Ward Hill, Mass.) in 691 grams of deionized water.Solution A was slowed poured into a well-stirred solution B, resultingin precipitate formation. After aging the suspension for 1 hour, theparticles were recovered by centrifugation at 1500-2000 rpm. Theprecipitate was then resuspended in 250 mL of ethanol (Alfa Aesar, WardHill, Mass.) followed by centrifugation to remove water, impuritycations/anions. This washing step was repeated. The precipitate wasdried in air at 25° C., ground to a fine powder using a mortar andpestle, and calcined to 800° C. for 2 hours in air. The sample waspelletized, crushed, and screened to 30-50 mesh prior to SHC testing.

[0200] 1.0 grams of steamed OlefinsMax (prepared as described inExample 1) was physically mixed with 0.5 grams of SHC catalyst and 2.0gram of SiC, and loaded into a fixed bed reactor. All other testingconditions were kept the same as in Example 1. Table 8 shows the resultsof the SHC test. TABLE 8 SHC Catalyst In_(0.9)Zn_(0.1)MnO₃In_(0.95)Cu_(0.05)MnO₃ % Conversion 8.9 8.1 C₁-C₄ Yield (wt %) 7.1 6.1H₂ Yield (wt %) 0.010 0.0038 % H₂ Conversion 78 91 CO_(x) Yield (wt %)0.012 0.158 % H₂ Selectivity 97 71

[0201] The data in Table 8 demonstrate that significant reductions inhydrogen yield can be achieved through the addition of SHC catalyst.Compared to Example 1, there is a 91 percent reduction in hydrogen yieldat similar hydrocarbon conversion and C1-C4 yields. Moreover, the SHCcatalyst exhibits a high selectivity of 71 percent for hydrogencombustion, resulting in minimal CO_(x) formation through non-selectivehydrocarbon activation.

Example 15

[0202] Table 9 shows the performance of additional combinations ofsub-group 3 SHC catalysts with the cracking catalyst of Example 1. Alltests were run at the conditions described in Example 1 with 0.5 gramsof the SHC catalyst being tested mixed with 2.0 grams of SiC and either1.0 grams of steamed OlefinsMax or 0.5 grams of fresh OlefinsMax. TABLE9 Catalyst Composition % H₂ Conversion % H₂ SelectivityIn_(0.975)Cu_(0.025)MnO₃ 93.1 64 Mn_(0.8)Co_(0.2)O₂ 86.1 56In_(0.9)Zn_(0.1)Mn_(0.8)Al_(0.2)O₃ 85.8 84 Mn_(0.7)Zn_(0.3)O₂ 85.7 37In_(0.9)Zn_(0.1)MnO₃ 84.9 90 Mn_(0.9)Zn_(0.1)O₂ 84.1 78Mn_(0.8)Zn_(0.2)O₂ 81.6 93 Mn_(0.72)Zn_(0.18)Al_(0.1)O₂ 80.9 94 InMnO₃80.4 93 Mn_(0.8)Zn_(0.1)Al_(0.1)O₂ 77.6 100In_(0.67)Mn_(0.67)Al_(0.67)O₃ 75.3 68 In_(0.95)Cu_(0.05)MnO₃ 72.6 64In_(0.8)Cu_(0.2)MnO₃ 72.3 60 Mn_(0.72)Zn_(0.18)Ti_(0.1)O₂ 68.1 92

Example 16

[0203] This example illustrates the hydrogen yield during hydrocarboncracking using a metal-based selective hydrogen combustion material withsignificant sulfur content. Sulfur was added to the metal-basedcomponent during reduction-oxidation cycles due to the presence of 0.99wt % sulfur in the gas oil feed. The catalyst mixture consisted of 8.1grams of equilibrated FCC catalyst (Beaumont ADA catalyst), 0.9 grams ofOlefinsMax (Grace Davison Division of W.R. Grace & Co.) which had beensteamed at 1500° F. (816° C.) for 16 hours, and 0.9 grams ofMg_(0.25)Na_(z)MnO_(x) material (60-100 mesh powder), the metal-basedcomponent. Each cycle consisted of hydrocarbon cracking by the FCC andOlefinsMax catalysts and hydrogen oxidation by the metal-basedcomponent, followed by air regeneration to remove coke deposited fromthe catalyst surface and re-oxidation of the metal-based component.During both cracking and regeneration, the catalyst particles were keptin a fluidized state by nitrogen co-feed. Vacuum gas oil (Baton RougeHot Cat) was used as hydrocarbon feed, and was injected at 1.2 g/min for75 sec through the fluidized catalyst bed at 1035° F. (557° C.)resulting in an overall catalyst-to-oil ratio of approximately 6. Theproduct gas was cooled, and liquid and vapor fractions were separatedand analyzed via gas chromatography. The coked catalyst system wasregenerated by addition of air at 1250° F. (677° C.). After regenerationwas complete, the cracking and regeneration cycle was repeated. After 4cycles, the catalyst mixture was removed from the reactor, themetal-based component was separated from the zeolite using a 100 meshsieve, and the amount of sulfur added to the metal-based component wasanalyzed by X-ray Fluorescence (XRF). It was found that the metal-basedcomponent contained 4.3 wt. % sulfur, and testing for selective hydrogencombustion indicated conversion was 70% and selectivity for H2 was 69%.

[0204] Example 16 shows that at least some of the crystal structureswill incorporate sulfur through exposure to sulfur in the feedstock. Itfurther demonstrates that crystal structures incorporating sulfur remaineffective for selective hydrogen combustion.

Example 17

[0205] This example illustrates the use of selective hydrogen combustionfor the production increase of propylene and butylene in a typical FCCunit. The study was done using computer yield simulation. The base casesimulates a cracking catalyst composed of 97 wt % FCC base catalyst and3% ZSM-5 additive catalyst, which is a fairly common catalyst blend forFCC units. The volumetric yields of the cracked products are listed inTable 15. The base case is compared to a selective-hydrogen-combustioncase, in which the ZSM-5 additive was raised to 7.6 wt % in addition topresence of 5 wt % selective hydrogen combustion catalyst. The productyields are also listed in Table 10. It is seen that the selectivehydrogen combustion catalyst can reduce the hydrogen concentration inthe product stream to near zero. This reduction frees vapor handlingcapacity downstream of the quench and initial vapor liquid separation,which can then be used for additional light olefins. Light olefinproduction is limited by vapor handling capacity and can readily beincreased by use of additional olefin selective cracking catalyst, suchas ZSM-5. As a result, it is possible to increase propylene and butyleneproduction from 421.3 to 503.8 kg.mole/hr and from 462.7 to 524.0kg.mole/hr, respectively. As the results indicate, the productionincrease is accomplished at a constant total volume of light gases,essentially overcoming the compressor and/or fractionator volumetriclimitations without any investments in the equipment. TABLE 10 SelectiveHydrogen Base Case Combustion Case (97% Base Catalyst + (87.4% BaseCatalyst + 3% ZSM-5 7.6% ZSM-5 Additive + Additive) 5% SHC Additive)Yields, Yields, Yields Products kg · mole/hr kg · mole/hr Δ, kg· mole/hrH2 143.8 0 −143.8 CH4 193.6 193.6 C2 180.7 190.7 C3 421.3 503.8 +82.5 C4462.7 524.0 +61.3 Σ C4-volume Δ = 0 Naphtha 948.2 883.1 −65.1 Heavy258.4 258.4 H2O 245.8 389.6 +143.8

[0206] In this process of converting hydrogen to water, the mixed metaloxide gets reduced or becomes oxygen-deficient due to the utilization ofits lattice oxygen needed to oxidize hydrogen. During catalystregeneration, the reduced mixed metal oxide is oxidized by NO_(x) and inthe process converts NO_(x) to N₂. This approach is different fromconventional de-NO_(x) additives to FCC, which do not perform hydrogencombustion (hence, do not undergo bulk reduction) in the riser. Afterthe mixed metal oxide is re-oxidized to its original state, it is fedback to the riser as described above for repeated reduction by hydrogen.

[0207] No modifications to the regeneration process are required forrealization of NO_(x) reduction during catalyst regeneration performedin existing fluid catalytic cracking (FCC) reactors. The combinedriser-regenerator arrangement allows the mixed metal oxide to undergorepeated reduction-oxidation cycles, thereby performing both SHC andde-NO_(x) functions over many cycles.

Example 18

[0208] A base case experiment was first conducted to measure the amountof NO_(x) generated during regeneration of a base FCC cracking catalyst.1.0 gram of spent (coked) FCC catalyst (obtained from Baton Rougerefinery) was physically mixed with 0.5 gram of OlefinsMax (spent samplefrom 2-methylpentane testing) and approximately 10 grams of siliconcarbide (<120 grit) and the mixture was heated to 700° C. in 150 cc/minof helium. The catalyst was allowed to equilibrate at 700° C. for 1 hourprior to substituting helium by a feed stream consisting of 150 cc/minof 33% air and balance helium. The reactor effluent was analyzed using achemiluminescence detector (Eco Physics CLD 70S NO analyzer) until theNO_(x) elution was complete.

[0209] The performance of the de-NO_(x) additive was tested byphysically-blending 0.5 gram of spent La_(0.6)Ca_(0.4)Mn_(0.4)Co_(0.6)O₃perovskite SHC catalyst (from 2-methylpentane testing), 0.5 gram ofspent OlefinsMax, 1.0 gram of coked FCC catalyst, and approximately 10grams of silicon carbide. All other testing conditions were kept thesame as in the base case. FIG. 1 shows the measured NO concentration inthe reactor effluent with reaction time for the spent SHC catalyst(solid line) compared to the base case (dotted line). It is evident thataddition of the perovskite catalyst decreases the net NOx generatedduring regeneration. The net amount of NO generated was reduced by 68%when spent La_(0.6)Ca_(0.4)Mn_(0.4)Co_(0.6)O₃ perovskite was added.

Example 19

[0210] Other test data showing the effect of the metal-based componenton NO_(x) reduction are contained in Table 11. TABLE 11 CatalystComposition % NO_(x) Conversion In_(0.95)Cu_(0.5)MnO₃ 62Mn_(0.8)Co_(0.2)O_(x) 59 Mn_(0.7)Zn_(0.3)O_(x) 55 In_(0.8)Zn_(0.2)MnO₃39 In_(0.9)Zn_(0.1)MnO₃ 26 In_(0.975)Cu_(0.025)MnO₃ 24Mg_(0.25)Na_(z)MnO_(x) 73 LaMn_(0.4)Ni_(0.4)Al_(0.2)O₃ 47La_(0.2)Co_(0.8)MnO₃ 47

We claim:
 1. A catalyst system comprising: (1) at least one solid acidcomponent and (2) at least one metal-based component, said metal-basedcomponent consisting essentially of (a) a metal combination selectedfrom the group consisting of: i) at least one metal from Group 3 and atleast one metal from Groups 4-15 of the Periodic Table of the Elements;ii) at least one metal from Groups 5-15 of the Periodic Table of theElements, and at least one metal from at least one of Groups 1, 2, and 4of the Periodic Table of the Elements; iii) at least one metal fromGroups 1-2, at least one metal from Group 3, and at least one metal fromGroups 4-15 of the Periodic Table of the Elements; and iv) two or moremetals from Groups 4-15 of the Periodic Table of the Elements and (b) atleast one of oxygen and sulfur, wherein the at least one of oxygen andsulfur is chemically bound both within and between the metals.
 2. Thecatalyst of system of claim 1 wherein the metal-based component is acombination of at least one of oxygen and sulfur, at least one metalselected from Group 3, and at least one metal selected from Groups 4-15of the Periodic Table of the Elements.
 3. The catalyst system of claim2, wherein the at least one metal selected from Group 3 comprises atleast one of scandium, yttrium, lanthanum, cerium, samarium, ytterbiumand praseodymium; and the at least one metal selected from Groups 4-15comprises at least one of titanium, zirconium, niobium, molybdenum,tungsten, manganese, iron, cobalt, iridium, nickel, palladium, platinum,copper, zinc, aluminum gallium, indium, germanium, tin, antimony, andbismuth.
 4. The catalyst system of claim 3, wherein the at least onemetal selected from Group 3 comprises at least one of scandium, yttrium,lanthanum, and praseodymium and the at least one metal selected fromGroups 4-15 comprises at least one of titanium, zirconium, manganese,iron, cobalt, nickel, copper, zinc, aluminum, indium, and tin.
 5. Thecatalyst system of claim 2 wherein the at least one metal-basedcomponent comprises one or more of Y_(a)In_(b)Zn_(c)Mn_(d)O_(x±δ),La_(a)Mn_(b)Ni_(c)Al_(d)O_(x±δ), La_(a)Mn_(b)Al_(c)O_(x±δ),Sc_(a)Cu_(bi)Mn_(c)O_(x±δ), Sc_(a)Zn_(b)Mn_(c)O_(x±δ),La_(a)Zr_(b)O_(x±δ), Mn_(a)Sc_(b)O_(x±δ), and Pr_(a)In_(b)Zn_(c)O_(x±δ),where a, b, c, and d are each between 0 and 1, the sum of a through dequals 1 to 3, x is the sum of a through d plus 1, and δ is the vacancyconcentration or excess oxygen concentration.
 6. The catalyst of systemof claim 1 wherein the metal-based component is a combination of atleast one of oxygen and sulfur, at least one metal selected from Groups5-15, and at least one metal selected from Groups 1, 2, and 4 of thePeriodic Table of the Elements.
 7. The catalyst system of claim 6,wherein the at least one metal selected from Groups 5-15 comprises atleast one of niobium, molybdenum, tungsten, manganese, iron, cobalt,iridium, nickel, palladium, platinum, copper, zinc, aluminum, gallium,indium, germanium, tin, antimony, and bismuth; the at least one metalselected from Groups 1 and 2 comprises at least one of sodium,potassium, magnesium, calcium, strontium, and barium; and the at leastone metal selected from Group 4 comprises at least one of titanium andzirconium.
 8. The catalyst system of claim 7, wherein the at least onemetal selected from Groups 5-15 comprises at least one of manganese,iron, cobalt, nickel, zinc, aluminum, indium, tin, antimony, andbismuth; the at least one metal selected from Groups 1 and 2 comprisesat least one of sodium, potassium, magnesium, calcium, strontium, andbarium; and the at least one metal selected from Group 4 comprises atleast one of titanium and zirconium.
 9. The catalyst system of claim 7wherein the at least one metal-based component comprises one or more ofK_(a)Ba_(b)Mn_(c)O_(x±δ), K_(a)Mg_(b)Mn_(c)O_(x±δ),Na_(a)Mg_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)O_(x±δ),K_(a)Sr_(b)Mn_(c)O_(x±δ), In_(a)Ca_(b)Mn_(c)O_(x±δ),Bi_(a)Ca_(b)Mn_(c)Co_(d)O_(x±δ), Bi_(a)Ca_(b)Mn_(c)Ni_(d)O_(x±δ),Ca_(a)Mn_(b)Sn_(c)Co_(d)O_(x±δ), In_(a)Mg_(b)Mn_(c)Al_(d)O_(x±δ),In_(a)Zn_(b)Mn_(c)Al_(d)O_(x±δ), Na_(a)Ba_(b)Mn_(c)O_(x±δ),Na_(a)Co_(b)Mn_(c)O_(x±δ), Ca_(a)Mn_(b)Sb_(c)O_(x±δ),Ca_(a)Mn_(b)Co_(c)Al_(d)O_(x±δ), Sr_(a)Sb_(b)Sn_(c)Mg_(d)O_(x±δ),K_(a)Co_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)O_(x±δ),Ni_(a)Mg_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)Al_(c)O_(x±δ),Mn_(a)Mg_(b)Ti_(c)O_(x±δ), Sr_(a)Sb_(b)Ca_(c)O_(x±δ),Sr_(a)Ti_(b)Sn_(c)Al_(d)O_(x±δ), Sr_(a)Mn_(b)Ti_(c)Al_(d)O_(x±δ),Ca_(a)Mn_(b)O_(x±δ), Ca_(a)Mn_(b)O_(x±δ), Ca_(a)Zr_(b)Al_(c)O_(x±δ),Bi_(a)Ca_(b)Mn_(c)O_(x±δ), Bi_(a)Sr_(b)Co_(c)Fe_(d)O_(x±δ),Ba_(a)Mn_(b)O_(x±δ), Ca_(a)Mn_(b)Al_(c)O_(x±δ),Ca_(a)Na_(b)Sn_(c)O_(x±δ), and Ba_(a)Zr_(b)O_(x±δ), where a, b, c, and dare each between 0 and 1, the sum of a through d equals 1 to 3, x is thesum of a through d plus 1, and δ is the vacancy concentration or excessoxygen concentration.
 10. The catalyst of system of claim 1 wherein themetal-based component is a combination of at least one of oxygen andsulfur, at least one metal selected from Groups 1-2, at least one metalselected from Group 3, and at least one metal selected from Groups 4-15of the Periodic Table of the Elements.
 11. The catalyst system of claim10, wherein the at least one metal selected from Groups 1-2 comprises atleast one of sodium, potassium, magnesium, calcium, strontium, andbarium; the at least one metal selected from Group 3 comprises at leastone of scandium, yttrium, lanthanum, cerium, samarium, ytterbium, andpraseodymium; and the at least one metal selected from Groups 4-15comprises at least one of titanium, zirconium, niobium, molybdenum,tungsten, manganese, iron, cobalt, iridium, nickel, palladium, platinum,copper, zinc, aluminum, gallium, indium, germanium, tin, antimony, andbismuth.
 12. The catalyst system of claim 11, wherein the at least onemetal selected from Groups 1 and 2 comprises at least one of sodium,calcium, strontium and barium; the at least one metal selected fromGroup 3 comprises at least one of scandium, yttrium, and lanthanum; andthe at least one metal selected from Groups 4-15 comprises at least oneof titanium, manganese, iron, cobalt, nickel, copper, aluminum, gallium,and tin.
 13. The catalyst system of claim 11 wherein the at least onemetal-based component comprises one or more ofLa_(a)Ca_(b)Mn_(c)Co_(d)Ti_(e)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Sn_(e)O_(x±δ), La_(a)Ca_(b)Co_(c)O_(x±δ),La_(a)Ca_(b)Mn_(c)Ni_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Co_(d)Sn_(e)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Al_(e)O_(x±δ), La_(a)Ca_(b)Mn_(c)Co_(d)O_(x±δ),Ba_(a)K_(b)Bi_(c)La_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Ti_(d)Al_(e)O_(x±δ),La_(a)Ca_(b)Co_(c)Ni_(d)Al_(e)O_(x±δ), La_(a)Ca_(b)Co_(c)Ti_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)O_(x±δ), Ba_(a)Bi_(b)La_(c)O_(x±δ),La_(a)Ca_(b)Mn_(c)Mg_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Fe_(d)O_(x±δ),La_(a)Sr_(b)Co_(c)Al_(d)O_(x±δ), Ba_(a)Bi_(b)Yb_(c)O_(x±δ),Ba_(a)Bi_(b)Sn_(c)La_(d)O_(x±δ), La₈Ca_(b)Mn_(c)Ga_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)Sn_(d)Al_(e)O_(x±δ), La_(a)Ca_(b)Mn_(c)Cu_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Ga_(e)O_(x±δ), La_(a)Ca_(b)Mn_(c)Al_(d)O_(x±δ),La_(a)Ca_(b)Co_(c)Al_(d)O_(x±δ), Ba_(a)Bi_(b)Sn_(c)La_(d)O_(x±δ),La_(a)Ca_(b)Fe_(c)Co_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Ni_(e)Al_(f)O_(x±δ), Y_(a)Ca_(b)Mn_(c)O_(x±δ),La_(a)Ca_(b)Fe_(c)Co_(d)O_(x±δ), and Sr_(a)Na_(b)Sn_(c)Y_(d)O_(x±δ),where a, b, c, d, e and f are each between 0 and 1, the sum of a throughf equals 1 to 3, x is the sum of a through f plus 1, and δ is thevacancy concentration or excess oxygen concentration.
 14. The catalystof system of claim 1 wherein the metal-based component is a combinationof at least one of oxygen and sulfur and at least two metals selectedfrom Groups 4-15 of the Periodic Table of the Elements.
 15. The catalystsystem of claim 14, wherein the at least two metals selected from Groups4-15 comprise at least one of titanium, zirconium, niobium, molybdenum,tungsten, manganese, iron, cobalt, iridium, nickel, palladium, platinum,copper, zinc, aluminum, gallium, indium, germanium, tin, antimony, andbismuth.
 16. The catalyst system of claim 15, wherein the at least twometals selected from Groups 4-15 comprise at least one of titanium,manganese, cobalt, copper, zinc, aluminum, and indium.
 17. The catalystsystem of claim 15 wherein the at least one metal-based componentcomprises one or more of In_(a)Cu_(b)Mn_(c)O_(x±δ), Mn_(a)Co_(b)O_(x±δ),In_(a)Zn_(b)Mn_(c)Al_(d)O_(x±δ), In_(a)Zn_(b)Mn_(c)O_(x±δ),Mn_(a)Zn_(b)O_(x±δ), Mn_(a)Zn_(b)Al_(c)O_(x±δ), In_(a)Mn_(b)O_(x±δ),In_(a)Mn_(b)Al_(c)O_(x±δ), and Mn_(a)Zn_(b)Ti_(c)O_(x±δ), where a, b, c,and d are each between 0 and 1, the sum of a through d equals 1 to 3, xis the sum of a through d plus 1, and δ is the vacancy concentration orexcess oxygen concentration.
 18. The catalyst system of claim 1, whereinthe metal-based component comprises at least one crystal structureselected from perovskite crystal structure, spinel crystal structure, orbirnessite crystal structure.
 19. The catalyst system of claim 18,wherein the metal-based component comprises at least one perovskitecrystal structure.
 20. The catalyst system of claim 1, wherein themetal-based component further comprises at least one of at least onesupport, at least one filler and at least one binder.
 21. The catalystsystem of claim 1, wherein the solid acid component is at least one ofone or more amorphous solid acids, one or more crystalline solid acids,one or more supported acids, and mixtures thereof.
 22. The catalystsystem of claim 1, wherein the solid acid component comprises at leastone molecular sieve.
 23. The catalyst system of claim 22, wherein themolecular sieve comprises at least one zeolite.
 24. The catalyst systemof claim 23, wherein the zeolite comprises at least one of MFI andfaujasite.
 25. The catalyst system of claim 24, wherein the zeolitecomprises at least one of ZSM-5 and Y zeolite.
 26. The catalyst systemof claim 22, wherein the molecular sieve comprises at least one ofcrystalline silicates, crystalline substituted silicates, crystallinealuminosilicates, crystalline substituted aluminosilicates, crystallinealuminophosphates, crystalline substituted aluminophosphates,zeolite-bound-zeolite, having 8- or greater-than-8 membered oxygen ringsin framework structures.
 27. The catalyst system of claim 26, whereincrystalline substituted aluminophosphates comprise SAPO, MeAPO, MeAPSO,ELAPO, and ELAPSO.
 28. The catalyst system of claim 1, wherein the solidacid component further comprises at least one of at least one support,at least one filler and at least one binder.
 29. The catalyst system ofclaim 1, wherein the solid acid component is in physical admixture withthe metal-based component.
 30. The catalyst system of claim 1, whereinthe solid acid component and the metal-based component are chemicallybound.
 31. The catalyst system of claim 1, wherein the weight ratio ofsolid acid component to the total weight of metal-based component is1:1000 to 1000:1.
 32. A process for treating a hydrocarbon feedstreamcomprising simultaneously contacting the feedstream under crackingconditions with a catalyst system comprising (1) at least one solid acidcomponent and (2) at least one metal-based component, said metal-basedcomponent consisting essentially of (a) a metal combination selectedfrom the group consisting of: i) at least one metal from Group 3 and atleast one metal from Groups 4-15 of the Periodic Table of the Elements;ii) at least one metal from Groups 5-15 of the Periodic Table of theElements, and at least one metal from at least one of Groups 1, 2, and 4of the Periodic Table of the Elements; iii) at least one metal fromGroups 1-2, at least one metal from Group 3, and at least one metal fromGroups 4-15 of the Periodic Table of the Elements; and iv) two or moremetals from Groups 4-15 of the Periodic Table of the Elements and (b) atleast one of oxygen and sulfur, wherein the at least one of oxygen andsulfur is chemically bound both within and between the metals.
 33. Thecatalyst of system of claim 32 wherein the metal-based component is acombination of at least one of oxygen and sulfur, at least one metalselected from Group 3, and at least one metal selected from Groups 4-15of the Periodic Table of the Elements.
 34. The catalyst of system ofclaim 32 wherein the metal-based component is a combination of at leastone of oxygen and sulfur, at least one metal selected from Groups 5-15,and at least one metal selected from Groups 1, 2, and 4 of the PeriodicTable of the Elements.
 35. The catalyst of system of claim 32 whereinthe metal-based component is a combination of at least one of oxygen andsulfur, at least one metal selected from Groups 1-2, at least one metalselected from Group 3, and at least one metal selected from Groups 4-15of the Periodic Table of the Elements.
 36. The catalyst of system ofclaim 32 wherein the metal-based component is a combination of at leastone of oxygen and sulfur and at least two metals selected from Groups4-15 of the Periodic Table of the Elements.
 37. The process of claim 32,wherein the hydrocarbon feedstream is cracked and the resultant hydrogensimultaneously combusted.
 38. The process of claim 37, wherein saidhydrogen combustion comprises selective hydrogen combustion.
 39. Theprocess of claim 38, wherein the selective hydrogen combustion isanaerobic selective hydrogen combustion without the feeding offree-oxygen containing gas into the reactor.
 40. The process of claim38, wherein the selective hydrogen combustion is conducted with thefeeding of free-oxygen containing gas into the reactor.
 41. The processof claim 32, wherein the catalyst system is regenerated periodically.42. The process of claim 32, wherein the solid acid component is atleast one of one or more amorphous solid acids, one or more crystallinesolid acids, one or more supported acids and mixtures thereof.
 43. Theprocess of claim 32, wherein the solid acid component comprises at leastone molecular sieve.
 44. The process of claim 32, wherein the weightratio of solid acid component to the total weight of metal-basedcomponent is 1:1000 to 1000:1.
 45. The process of claim 32, wherein theprocess temperature is from about 300 to about 800° C.
 46. The processof claim 32, wherein the process pressure is from 0.1 to 10 atmospheres(10 to 1000 kPa).
 47. The process of claim 32 wherein the catalystsystem to oil ratio is from 0.01 to
 1000. 48. The process of claim 32,which produces liquid and gaseous hydrocarbons.
 49. The process of claim32, wherein the solid acid component is at least one cracking catalystand the metal-based component is at least one selective hydrogencombustion catalyst.
 50. The process of claim 49, wherein the crackingcatalyst is at least one of at least one fluid catalytic cracking basecatalyst, at least one fluid catalytic cracking additive catalyst, andmixtures thereof.
 51. The process of claim 32, wherein the added heat isreduced compared to the added heat required in a process for treating ahydrocarbon feedstream operated under the same conditions without ametal-based component in the catalyst system.
 52. The process of claim51, wherein the added heat is less than 90% of the added heat requiredin a process for treating a hydrocarbon feedstream operated under thesame conditions without a metal-based component in the catalyst system.53. The process of claim 32, wherein the hydrocarbon feedstreamcomprises at least one of gas oil, steam cracked gas oil and residues;heavy hydrocarbonaceous oils comprising materials boiling above 566° C.;heavy and reduced petroleum crude oil, petroleum atmosphericdistillation bottom, petroleum vacuum distillation bottom, heating oil,pitch, asphalt, bitumen, other heavy hydrocarbon residues, tar sandoils, shale oil, liquid products derived from coal liquefactionprocesses, steam heating oil, jet fuel, diesel, kerosene, gasoline,coker naphtha, steam cracked naphtha, catalytically cracked naphtha,hydrocrackate, reformate, raffinate reformate, Fischer-Tropsch liquids,Fischer-Tropsch gases, natural gasoline, distillate, virgin naphtha, C₅₊olefins, C₅₊ paraffins, ethane, propane, butanes, butenes and butadiene,olefinic or paraffinic feedstreams.
 54. The process of claim 53, whereinthe feedstream comprises at least one of paraffins, olefins, aromatics,or naphthenes
 55. A process comprising: (A) charging at least onehydrocarbon feedstream to a fluid catalytic cracking reactor, (B)charging a hot fluidized cracking/selective hydrogen combustion catalystsystem from a catalyst regenerator to said fluid catalytic crackingreactor, said catalyst system comprising (1) at least one solid acidcomponent and (2) at least one metal-based component, said metal-basedcomponent consisting essentially of (a) a metal combination selectedfrom the group consisting of: i) at least one metal from Group 3 and atleast one metal from Groups 4-15 of the Periodic Table of the Elements;ii) at least one metal from Groups 5-15 of the Periodic Table of theElements, and at least one metal from at least one of Groups 1, 2, and 4of the Periodic Table of the Elements; iii) at least one metal fromGroups 1-2, at least one metal from Group 3, and at least one metal fromGroups 4-15 of the Periodic Table of the Elements; and iv) two or moremetals from Groups 4-15 of the Periodic Table of the Elements and (b) atleast one of oxygen and sulfur, wherein the at least one of oxygen andsulfur is chemically bound both within and between the metals; (C)catalytically cracking said feedstream(s) and combusting resultanthydrogen at about 300 to about 800° C. in the presence of said catalystsystem to produce a stream of cracked products and uncracked feed and aspent catalyst system which are discharged from said reactor, (D)separating a phase rich in said cracked products and uncracked feed froma phase rich in said spent catalyst system, (E) stripping said spentcatalyst system at stripping conditions to produce a stripped catalystphase, (F) decoking and oxidizing said stripped catalyst phase in acatalyst regenerator at catalyst regeneration conditions to produce saidhot fluidized cracking/selective hydrogen combustion catalyst system,which is recycled to the said reactor, and (G) separating and recoveringsaid cracked products and uncracked feed.
 56. The process of claim 55,wherein NO_(x) emissions are reduced below the level of NO_(x) emissionsresulting from regeneration of the fluidized cracking catalyst withoutthe metal-based component.
 57. The process of claim 56 wherein NO_(x)emissions are reduced below 50% of the level of NO_(x) emissionsresulting from regeneration of the fluidized cracking catalyst withoutthe metal-based component.
 58. The catalyst of system of claim 55wherein the metal-based component is a combination of at least one ofoxygen and sulfur, at least one metal selected from Group 3, and atleast one metal selected from Groups 4-15 of the Periodic Table of theElements.
 59. The catalyst of system of claim 55 wherein the metal-basedcomponent is a combination of at least one of oxygen and sulfur, atleast one metal selected from Groups 5-15, and at least one metalselected from Groups 1, 2, and 4 of the Periodic Table of the Elements.60. The catalyst of system of claim 55 wherein the metal-based componentis a combination of at least one of oxygen and sulfur, at least onemetal selected from Groups 1-2, at least one metal selected from Group3, and at least one metal selected from Groups 4-15 of the PeriodicTable of the Elements.
 61. The catalyst of system of claim 55 whereinthe metal-based component is a combination of at least one of oxygen andsulfur and at least two metals selected from Groups 4-15 of the PeriodicTable of the Elements.
 62. The process of claim 55, wherein thecracking/selective hydrogen combustion catalyst system comprises aphysical mixture of at least one fluid catalytic cracking catalystcomponent and at least one selective hydrogen combustion catalystcomponent.
 63. The process of claim 55, wherein the catalytic crackingcatalyst component comprises at least one of a fluid catalytic crackingbase catalyst component and a fluid catalytic cracking additive catalystcomponent.
 64. The process of claim 63, wherein the fluid catalyticcracking additive catalyst component is at least one of anoctane-boosting additive, a metal passivation additive, a CO oxidationadditive, a coke oxidation additive, an SOx reduction additive, a NOxreduction additive, or mixture thereof.
 65. The process of claim 55,wherein the cracking/selective hydrogen combustion catalyst systemcomprises at least one fluid catalytic cracking catalyst componentchemically bound to at least one selective hydrogen combustion catalystcomponent.
 66. The process of claim 65, wherein the fluid catalyticcracking catalyst component comprises at least one of a fluid catalyticcracking base catalyst component and a fluid catalytic cracking additivecatalyst component.
 67. The process of claim 66, wherein the additivecatalyst component is at least one of octane-boosting additives, metalpassivation additives, CO oxidation additives, coke oxidation additives,SOx reduction additives, NO_(x) reduction additives, and mixturesthereof.
 68. A process comprising contacting at least one hydrocarbonfeedstream with a cracking/selective hydrogen combustion catalyst systemunder effective catalytic reaction conditions to produce liquid and/orgaseous products comprising cracked hydrocarbons, wherein the yield ofhydrogen is less than the yield of hydrogen when contacting saidhydrocarbon feedstream(s) with said cracking catalyst alone under saidcatalytic reaction conditions.
 69. The process of claim 68 wherein thecracking/selective hydrogen combustion catalyst system is regeneratedwith lower NO_(x) concentrations in the resulting flue gas than withregeneration of the cracking catalyst alone.